CS_SI_Final_Rev1.pdf

Transcription

1 Supporting Information Stereoretentive C(sp 3 ) S Cross-Coupling Feng Zhu, a# Eric Miller, a# Shuo-qing Zhang, b Duk Yi, a Sloane O Neill, a Xin Hong, b * Maciej A. Walczak a * a Department of Chemistry, University of Colorado, Boulder, CO 80309, United States b Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang , P. R. China *hxchem@zju.edu.cn *maciej.walczak@colorado.edu S1

2 Table of Contents 1. General Information... S3 2. General Procedures... S4 3. Detailed Experimental Procedures for Compounds S4 4. Detailed Experimental Procedures for Compounds S1-S31... S28 5. Detailed Procedure for Protecting Group Removal... S43 6. Procedures for Mechanistic Studies... S43 7. Computational Details... S44 8. Additional Computational Results... S45 9. Cartesian Coordinates of Optimized Structures... S References... S Copies of 1D and 2D NMR Spectra... S121 S2

3 All chemicals were purchased as reagent grade and used without further purification unless otherwise noted. Solvents were filtered through a column of activated alumina prior to use. All reactions were carried out under anhydrous N2 in oven-dried glassware. m-xylene was distilled under nitrogen over sodium and degassed prior to use. Anhydrous 1,4-dioxane, Anhydrous 1,2-dichloroethane, JackiePhos, and CuCl were purchased from Sigma-Aldrich. Anhydrous KF was purchased from Strem Chemicals, Inc. Visualizations were performed with UV light and/or Hanessian stain and/or sulfuric acid stain (5% H2SO4 in MeOH). Column chromatography was performed on silica gel ( mesh). 1 H and 13 C NMR spectra were recorded on Bruker/Varian 300/400/500 MHz instruments and are reported as follows: chemical shift (δ), multiplicity (s = singlet, d = doublet, t = triplet, q =quartet, br = broad, m = multiplet), coupling constants (Hz), and integration. The residual solvent reference peaks were used from published literature. 2D NMR experiments were performed using standard parameters (200 and More NMR Experiments, S. Berger, S. Braun, Wiley-VCH, 2004). IR measurements were performed on Agilent Cary 630 FT/IR instrument and optical rotations were measured on JASCO P-1030 and are reported as average of five data points. High-resolution mass spectra (HR-MS) were recorded on a Waters Synapt G2 HDMS q-tof hybrid mass spectrometer. S3

4 General Procedure A for Cross-Coupling Reactions Anomeric stannane ( equiv), disulfide (1.00 equiv), and CuCl (300 mol%) were added to a one dram vial with a screw-top septum, and the vial was then evacuated and refilled with N2 (3x). Anhydrous m- xylene and 1,2-dichloroethane (2:1, 3.00 ml) were added and the reaction mixture was heated in an oil bath (130 o C) for the indicated period of time, cooled to rt, filtered through a pad of Celite, and concentrated. 1 H NMR spectra were recorded using this mixture to evaluate diastereoselectivity. The crude material was purified by column chromatography on SiO2. General Procedure B for Cross-Coupling Reactions Anomeric stannane ( equiv), succinimide (1.00 equiv), and CuCl (300 mol%) were added to a one dram vial with a screw-top septum, and the vial was then evacuated and refilled with N2 (3x). Anhydrous m- xylene and 1,2-dichloroethane (2:1, 3.00 ml) were added and the reaction mixture was heated in an oil bath (110 or 130 o C) for the indicated period of time, cooled to rt, filtered through a pad of Celite, and concentrated. 1 H NMR spectra were recorded using this mixture to evaluate diastereoselectivity. The crude material was purified by column chromatography on SiO2. General Procedure C for the Preparation of Disulfanes Sodium perborate monohydrate (2.00 equiv.) was added to a stirring solution of aromatic thiol (1.00 equiv.) in a 2.5:1 AcOH/H2O solution (0.250 M). The resulting solution was stirred at ambient temperature for 4 hours. The crude mixture was concentrated in vacuo and purified via flash chromatography on silica. General Procedure D for Preparation of N-thio-pyrrolidine-2,5-diones To a flame-dried round bottom flask was charged N-chlorosuccinimide (1.05 equiv.) and anhydrous CH2Cl2 (0.250 M). The mixture was cooled to 0 C and aliphatic or aromatic thiol (1.00 equiv.) in anhydrous CH2Cl2 (1.00 M) was added dropwise via syringe pump over minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (1.10 equiv.) in CH2Cl2 (1.00 M) via syringe pump over minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried, filtered, and concentrated. The crude material was purified via flash chromatography on silica. Phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (10). 1 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1,2- diphenyldisulfane (21.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m- xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 10:1) 10 (45.6 mg, 72%) as a white solid: = +6.9 (c = 0.40, CHCl3); IR (ATR) ν = 3030, 2862, 1477, 1359, 1278, 1066, 909, 735, 696 cm - 1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 18H), (m, 5H), S4

5 (m, 4H), 4.74 (d, J = 10.3 Hz, 1H), 4.68 (d, J = 9.7 Hz, 1H), (m, 3H), (m, 4H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 138.6, 138.5, 138.2, 134.0, 132.1, 129.0, (2), 128.5, 128.4, 128.1, 128.0, 127.9, (2), 127.7, 127.6, 87.6, 86.9, 81.0, 79.3, 78.0, 76.0, 75.6, 75.2, 73.6, 69.2; HRMS (ESI) m/z calcd for C40H40O5SNa [M + Na] , found Fluorophenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (14). 3 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol 1,2-bis(4- fluorophenyl)disulfane S1 (25.4 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 14 (47.5 mg, 73%) as a white foam: = +5.7 (c = 0.35, CHCl3); IR (ATR) ν = 3030, 2863, 1588, 1490, 1453, 1359, 1223, 1066, 909, 832, 735, 697 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 18H), 7.19 (dd, J = 7.1, 2.5 Hz, 2H), (m, 2H), (m, 4H), 4.75 (d, J = 10.3 Hz, 1H), (m, 4H), (m, 3H), 3.63 (t, J = 9.1 Hz, 1H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 138.5, 138.4, 138.2, 138.1, 135.0, 134.8, 128.6, 128.6, 128.5, 128.3, (2), 128.0, (2), 127.8, 116.2, 115.9, 87.8, 86.9, 81.0, 79.1, 77.9, 76.0, 75.6, 75.2, 73.6, 69.2; 19 F NMR (282 MHz, CDCl3) δ ; HRMS (ESI) m/z calcd for C40H39O5SFNa [M + Na] , found Methylphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (15). 4 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1,2- bis(4-methylphenyl)disulfane (24.6 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 15 (45.3 mg, 70%) as a yellow solid. Characterization data matched the literature report. 4 4-(tert-Butyl)phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (16). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol 1,2-bis(4- (tert-butyl)phenyl)disulfane S2 (33.0 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 16 (59.2 mg, 86%) as a colorless oil: = +2.9 (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2956, 2864, 1488, 1453, 1359, 1268, 1208, 1063, 908, 829, 733, 696, 614 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 18H), (m, 4H), (m, 4H), 4.69 (d, J = 10.3 Hz, 1H), (m, 4H), (m, S5

6 4H), (m, 2H), 1.25 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 150.8, 138.5, 138.3, 138.2, 132.2, 130.2, (2), (3), 128.4, 128.1, (3), (2), 127.8, 127.7, 126.1, 87.7, 86.9, 80.9, 79.2, 78.0, 76.0, 75.5, 75.2, 73.6, 69.3, 34.7, 31.4; HRMS (ESI) m/z calcd for C44H48O5SNa [M + Na] , found (Acetylamino)phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (17). 3 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), N,N'-(disulfanediylbis(4,1-phenylene))diacetamide S3 (33.2 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 1:1) 17 (56.5 mg, 82%) as a white foam: = -5.3 (c = 0.75, CHCl3); IR (ATR) ν = 3281, 3030, 1657, 1591, 1525, 1525, 1453, 1395, 1358, 1312, 1064, 908, 821, 735 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 20H), 7.19 (m, 3H), (m, 4H), 4.74 (d, J = 10.3 Hz, 1H), (m, 4H), (m, 4H), (m, 2H), 2.16 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 168.3, 138.5, 138.4, 138.2, 137.8, 133.7, (2), 128.5, 128.3, 128.1, 128.0, (2), (2), 127.7, 120.1, 87.8, 86.9, 81.0, 79.2, 77.9, 75.9, 75.5, 75.2, 73.5, 69.1, 24.8; HRMS (ESI) m/z calcd for C42H43O6SNNa [M + Na] , found Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (18). 3 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1,2- bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 18 (63.6 mg, 96%) as a colorless oil: = +2.3 (c = 0.25, CHCl3); IR (ATR) ν = 3028, 2861, 1590, 1492, 1453, 1358, 1284, 1244, 1062, 908, 827, 732, 695, 641 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 20H), (m, 2H), (m, 4H), 4.76 (d, J = 10.3 Hz, 1H), (m, 4H), (m, 7H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.9, 138.6, 138.5, 138.3, 138.2, 135.3, (2), 128.5, 128.3, 128.1, 128.0, (2), (2), 127.7, 123.6, 114.6, 88.0, 86.9, 80.9, 79.1, 78.0, 75.9, 75.5, 75.2, 73.6, 69.2, 55.4; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found (Trifluoromethoxy)phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (19). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), S6

7 1,2-bis(4-(trifluoromethoxy)phenyl)disulfane S5 (38.6 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 19 (40.0 mg, 56%) as a colorless oil: = (c = 0.70, CHCl3); IR (ATR) ν = 3031, 2865, 1490, 1453, 1255, 1207, 1160, 1063, 909, 844, 734, 695 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 18H), (m, 2H), (m, 2H), (m, 4H), 4.75 (d, J = 10.4 Hz, 1H), 4.65 (d, J = 9.7 Hz, 1H), (m, 3H), (m, 4H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 138.4, 138.3, 138.1, 138.0, 133.4, 132.6, (2), 128.5, 128.3, 128.1, 128.0, (2), (2), 121.4, 87.4, 86.8, 80.9, 79.2, 77.9, 76.0, 75.6, 75.2, 73.6, 69.2; 19 F NMR (282 MHz, CDCl3) δ -57.8; HRMS (ESI) m/z calcd for C41H39O6SF3Na [M + Na] , found Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (20). 3 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1-((3- methoxyphenyl)thio)pyrrolidine-2,5-dione S6 (23.7 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 20 (33.1 mg, 50%) as a colorless oil: = -1.0 (c = 0.90, CHCl3); IR (ATR) ν = 3030, 2863, 1588, 1453, 1359, 1248, 1065, 735, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 5H), (m, 1H), (m, 4H), 4.71 (dd, J = 12.2, 10.0 Hz, 2H), (m, 3H), (m, 7H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.9, 138.5, 138.3, (2), 135.2, 129.8, (2), (2), 128.3, 128.1, 128.0, (2), 127.8, 127.7, 124.0, 116.7, 113.9, 87.6, 86.9, 80.8, 79.3, 77.9, 76.0, 75.5, 75.2, 73.6, 69.2, 55.3; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found ,5-Dimethylphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (21). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol, 1,2- bis(3,5-dimethylphenyl)disulfane S7 (38.6 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 21 (40.9 mg, 62%) as a colorless oil: = (c = 0.20, CHCl3); IR (ATR) ν = 3030, 2908, 2863, 1581, 1453, 1360, 1278, 1210, 1069, 909, 847, 736, 697 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 4H), 6.86 (td, J = 1.6, 0.8 Hz, 1H), (m, 4H), 4.74 (d, J = 10.3 Hz, 1H), (m, 4H), (m, 4H), 3.51 (t, J = 9.1 Hz, 2H), 2.21 (s, 6H); 13 C NMR (75 MHz, CDCl3) δ 138.6, 138.6, 138.4, 138.3, 138.2, 133.4, 129.8, 129.5, 128.6, 128.6, 128.5, 128.5, 128.3, 128.1, 128.0, 128.0, 127.9, 127.9, 127.9, 127.8, 127.7, 87.9, 87.0, 81.1, 79.3, 78.0, 76.0, 75.5, 75.2, 73.6, 69.2, 21.3; HRMS (ESI) m/z calcd for C42H44O5SNa [M + Na] , found S7

8 3,4-Dimethoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (22). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1-((3,4- dimethoxyphenyl)thio)pyrrolidine-2,5-dione S8 (26.7 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 22 (41.5 mg, 60%) as a colorless oil: = -2.4 (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2902, 1582, 1501, 1453, 1252, 1134, 1062, 1062, 909, 731, 695 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 4H), 6.70 (d, J = 8.3 Hz, 1H), (m, 4H), 4.74 (d, J = 10.4 Hz, 1H), (m, 4H), 3.84 (s, 3H), (m, 3H), 3.66 (s, 3H), 3.63 (d, J = 9.0 Hz, 1H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 149.3, 149.0, 138.5, 138.3, (2), (3), 128.5, 128.2, 128.1, 128.0, 127.9, (2), 126.1, 124.1, 116.5, 111.4, 88.1, 87.0, 80.7, 79.1, 77.9, 75.9, 75.4, 75.2, 73.6, 69.3, 56.0, 55.9; HRMS (ESI) m/z calcd for C42H44O7SNa [M + Na] , found Naphthalenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (23). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1,2- di(naphthalen-2-yl)disulfane S9 (31.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 23 (49.9 mg, 73%) as a colorless foam: = +3.3 (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2863, 1587, 1496, 1453, 1358, 1272, 1209, 1065, 908, 815, 734, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 8.10 (d, J = 1.4 Hz, 1H), (m, 1H), (m, 3H), (m, 20H), (m, 2H), (m, 4H), (m, 2H), (m, 3H), (m, 4H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 138.5, 138.4, (2), 133.8, 132.6, 131.2, 131.1, 129.6, 128.6, 128.5, 128.3, 128.2, 128.1, 128.0, (3), (2), 127.7, 126.6, 126.3, 87.6, 86.9, 81.0, 79.3, 78.0, 76.0, 75.6, 75.2, 73.6, 69.2; HRMS (ESI) m/z calcd for C44H42O5SNa [M + Na] , found iso-Propyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (24). 5 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2- (isopropylthio)isoindoline-1,3-dione S10 (22.1 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 24 (24.6 mg, 41%) as a white solid: = (c = 4.40, CHCl3); IR (ATR) ν = 3030, 2863, 1587, 1496, 1453, S8

9 1358, 1272, 1209, 1065, 908, 815, 734, 696 cm -1 ; 1 H NMR (300 MHz CDCl3) δ (m, 18H), (m, 2H), (m, 4H), 4.72 (d, J = 10.2 Hz, 1H), (m, 4H), (m, 3H), 3.59 (t, J = 9.2 Hz, 1H), (m, 2H), 3.25 (p, J = 6.7 Hz, 1H), 1.37 (d, J = 5.8 Hz, 3H), 1.35 (d, J = 5.7 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 138.7, 138.4, 138.2, 128.6, (3), 128.1, (2), 127.8, 127.8, 127.7, 86.9, 84.8, 82.2, 79.2, 78.2, 75.9, 75.7, 75.2, 73.6, 69.4, 35.7, 24.2 (2); HRMS (ESI) m/z calcd for C37H42O5SNa [M + Na] , found Cyclohexyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (25). 6 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2- (cyclohexylthio)isoindoline-1,3-dione (26.1 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 25 (37.0 mg, 58%) as a white foam: = +4.5 (c = 0.35, CHCl3); IR (ATR) ν = 3029, 2925, 2851, 1496, 1450, 1357, 1264, 1207, 1063, 908, 818, 734, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), (m, 2H), (m, 2H), 4.72 (d, J = 10.2 Hz, 1H), (m, 4H), (m, 3H), 3.58 (t, J = 9.2 Hz, 1H), (m, 2H), 3.00 (tt, J = 10.6, 3.7 Hz, 1H), 2.05 (d, J = 12.8 Hz, 2H), 1.76 (dd, J = 10.2, 3.7 Hz, 2H), 1.59 (s, 1H), (m, 2H), (m, 3H); 13 C NMR (75 MHz, CDCl3) δ 138.7, 138.4, 138.3, 138.2, 128.6, (3), 128.1, 127.9, 127.8, 127.7, 86.9, 84.6, 82.2, 79.2, 78.2, 75.9, 75.7, 75.2, 73.5, 69.5, 44.0, 34.4, 34.3, 26.3, 26.1, 25.9; HRMS (ESI) m/z calcd for C40H46O5SNa [M + Na] , found (2-(Boc-amino)ethyl) 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (26). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), tertbutyl-(2-((2,5-dioxopyrrolidin-1-yl)thio)ethyl)carbamate S11 (27.3 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 110 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 26 (46.9 mg, 67%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3373, 3030, 2905, 1708, 1497, 1453, 1363, 1248, 1160, 1063, 909, 732, 696 cm-1; 1H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), 5.40 (s, 1H), (m, 5H), (m, 3H), 4.44 (d, J = 9.7 Hz, 1H), (m, 4H), (m, 4H), 2.92 (dt, J = 14.0, 5.9 Hz, 1H), 2.78 (dt, J = 14.1, 6.0 Hz, 1H), 1.44 (s, 9H); 13C NMR (75 MHz, CDCl3) δ 156.0, 138.6, 138.1, 138.1, 138.0, 128.6, 128.5, 128.4, 128.1, 128.0, 128.0, 128.0, 127.9, 127.8, 127.8, 86.7, 85.9, 81.6, 79.3, 78.9, 77.9, 75.9, 75.7, 75.2, 73.6, 69.1, 41.3, 32.3, 28.6; HRMS (ESI) m/z calcd for C41H49O7SNNa [M + Na] , found S9

10 2-((2-Ethylhexyl)oxycarbonyl)ethyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (26). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2-ethylhexyl-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate S12 (31.5 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 110 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 27 (49.6 mg, 67%) as a colorless oil: = +2.2 (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2927, 2861, 1732, 1454, 1359, 1279, 1131, 1064, 907, 733 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), 4.88 (qd, J = 10.9, 8.7 Hz, 4H), 4.75 (d, J = 10.3 Hz, 1H), (m, 3H), 4.49 (d, J = 9.7 Hz, 1H), (m, 2H), (m, 4H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 7H), (m, 6H); 13 C NMR (75 MHz, CDCl3) δ 172.2, 138.6, 138.3, 138.2, 138.0, 128.6, (3), 128.4, 128.1, 128.0, (2), 127.8, 127.7, 86.7, 85.6, 81.8, 79.2, 78.0, 75.9, 75.6, 75.2, 73.6, 69.1, 67.3, 38.8, 35.8, 30.5, 29.0, 26.2, 23.9, 23.1, 14.2, 11.1; HRMS (ESI) m/z calcd for C45H56O7SNNa [M + Na] , found (R)-2,8-Dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)-6-(((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6- ((benzyloxy)methyl)tetrahydro-2h-pyran-2-yl)thio)chromane (28). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1-(((R)-2,8- dimethyl-2-((4r,8r)-4,8,12-trimethyltridecyl)chroman-6-yl)thio)pyrrolidine-2,5-dione S13 (51.6 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4- dioxane (3.00 ml). The reaction mixture was heated under N2 at 110 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 15:1) 28 (64.0 mg, 68%) as a colorless oil: = (c = 11.0, CHCl3); IR (ATR) ν = 2925, 2866, 1458, 1363, 1223, 1070, 1033, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 16H), (m, 4H), (m, 5H), (m, 4H), (m, 3H), (m, 1H), (m, 2H), 2.59 (t, J = 6.8 Hz, 2H), 2.07 (s, 3H), (m, 2H), (m, 23H), (m, 13H); 13 C NMR (75 MHz, CDCl3) δ 152.7, 138.6, (2), 138.3, 134.0, 132.8, 128.6, (2), 128.3, 128.1, 128.0, (2), 127.8, 127.7, 127.1, 121.2, 121.1, 88.6, 87.0, 81.1, 79.3, 78.0, 76.6, 76.0, 75.4, 75.1, 73.7, 69.3, 40.4, 39.5, 37.6, 37.4, 32.9 (2), 31.1, 28.1, 24.9, 24.6, 24.4, 22.9, 22.8, 22.2, 21.1, 19.9, 19.8, 16.1; HRMS (ESI) m/z calcd for C61H80O6SNa [M + Na] , found S10

11 4-Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-glucopyranoside (33). According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 1,2- bis(4-methoxyphenyl)disulfide S5 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 33 (58.3 mg, 88%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2863, 1591, 1493, 1453, 1360, 1285, 1245, 1071, 827, 734, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 20H), (m, 2H), (m, 2H), 5.49 (d, J = 4.6 Hz, 1H), 5.03 (d, J = 10.9 Hz, 1H), (m, 3H), 4.71 (d, J = 11.7 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), 3.78 (s, 4H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.6, 138.9, 138.4, 138.1, 137.9, 134.9, 128.6, 128.5, 128.4, 128.3, 128.1, (3), 127.8, (2), 124.5, 114.7, 88.1, 82.6, 80.0, 77.8, 75.9, 75.2, 73.5, 72.6, 71.2, 68.9, 55.4; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranoside (34). According to the general protocol A, [2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl]tri-n-butylstannane 2 (122 mg, mmol), 1,2- bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 34 (74.0 mg, 91%) as a colorless oil: = +5.1 (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2863, 1591, 1493, 1453, 1359, 1284, 1244, 1089, 827, 731, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 20H), (m, 2H), 4.98 (d, J = 11.5 Hz, 1H), (m, 4H), 4.61 (d, J = 11.5 Hz, 1H), (m, 3H), 3.98 (d, J = 3.7 Hz, 1H), 3.88 (t, J = 9.4 Hz, 1H), 3.76 (s, 3H), (m, 2H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.6, 139.0, 138.6, 138.4, 138.1, 134.8, (2), 128.4, 128.3, 128.0, 127.9, (2), 127.7, 127.5, 124.2, 114.5, 88.5, 84.4, 77.5, 77.3, 75.7, 74.5, 73.7, 73.7, 72.8, 68.9, 55.4; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-galactopyranoside (35). According to the general protocol A, [2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl]tri-n-butylstannane 2 (122 mg, mmol), 1,2- bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 35 (37.8 mg, 88%) as a colorless oil: = (c = 11.50, CHCl3); IR (ATR) ν = 3033, 2869, 1596, 1495, 1458, 1290, 1249, 1100, 1070, 832, 739, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 22H), (m, 2H), 5.54 (d, J = 5.4 Hz, 1H), 4.98 (d, J = 11.5 Hz, 1H), 4.90 (d, J = 11.8 Hz, 1H), (m, 3H), 4.60 (d, J = 11.5 Hz, 1H), 4.53 (td, J = 6.2, 1.3 Hz, 1H), (m, 2H), 4.35 (dd, J = 10.0, 5.4 Hz, 1H), 4.00 (dd, J = 3.0, 1.3 Hz, 1H), 3.84 (dd, J = 10.0, 2.9 Hz, 1H), 3.74 (s, 3H), 3.56 (d, J = 6.3 Hz, 2H); 13 C NMR (75 S11

12 MHz, CDCl3) δ 159.6, 138.9, 138.8, 138.4, 138.3, 135.1, (2), 128.4, 128.3, 128.1, (2), (3), 124.6, 114.6, 88.7, 79.6, 76.8, 75.5, 74.9, 73.6, 73.5, 72.7, 70.4, 69.3, 55.4; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found Methoxyphenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside (36). According to the general protocol A, (2,3,4,5-tetra-O-benzyl-α-D-mannopyranosyl)tri-n-butylstannane (162 mg, mmol) S15, 1,2- bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 6:1) 36 (69.1 mg, 85%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2865, 1591, 1493, 1453, 1364, 1285, 1246, 1089, 1027, 828, 736, 697 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 22H), (m, 2H), 5.45 (d, J = 1.7 Hz, 1H), 4.93 (d, J = 10.9 Hz, 1H), (m, 8H), 4.35 (ddd, J = 9.7, 5.2, 2.2 Hz, 1H), (m, 2H), (m, 3H), 3.76 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 159.8, 138.6, 138.4, 138.1, 134.9, (3), 128.4, (2), 128.0, 127.9, (2), 127.8, 127.5, 126.6, 124.4, 114.7, 86.6, 80.3, 76.2, 75.3, 73.5, 72.8, 72.2, 72.0, 69.6, 55.5; HRMS (ESI) m/z calcd for C41H42O6SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-6-O-acetyl-1-thio-β-D-glucopyranoside (37). According to the general protocol A, (6-O-acetyl-2,3,4-tri-O-benzyl-β-D-glycopyranosyl)tri-n-butylstannane S16 (115 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 37 (35.7 mg, 58%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2900, 1740, 1591, 1493, 1454, 1362, 1242, 1064, 909, 829, 734, 697, 642 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 15H), (m, 2H), (m, 2H), (m, 2H), 4.76 (d, J = 10.3 Hz, 1H), 4.58 (d, J = 10.8 Hz, 1H), 4.52 (d, J = 9.7 Hz, 1H), 4.37 (dd, J = 11.8, 1.5 Hz, 1H), (m, 1H), 3.81 (s, 3H), 3.71 (t, J = 8.8 Hz, 1H), (m, 3H), 2.06 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 170.8, 160.0, 138.4, 138.1, 137.8, 135.5, 128.7, (2), 128.3, (2), 128.1, 127.9, 123.4, 114.5, 88.2, 86.9, 81.0, 77.7, 77.0, 76.0, 75.6, 75.2, 63.4, 55.5, 21.0; HRMS (ESI) m/z calcd for C36H38O7SNa [M + Na] , found S12

13 4-Methoxyphenyl 2,3,4-tri-O-benzyl-6-O-pivaloyl-1-thio-β-D-glucopyranoside (38). According to the general protocol A, (2,3,4-tri-O-benzyl-6-O-pivaloyl-β-D-glucopyranosyl)tri-n-butylstannane S17 (121 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 38 (55.2 mg, 84%) as a colorless oil: = -3.2 (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2958, 1728, 1591, 1493, 1360, 1283, 1244, 1144, 1063, 908, 828, 731, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 13H), (m, 2H), (m, 4H), 4.76 (d, J = 10.3 Hz, 1H), 4.59 (d, J = 10.6 Hz, 1H), 4.55 (d, J = 9.7 Hz, 1H), 4.47 (dd, J = 11.9, 1.3 Hz, 1H), (m, 1H), 3.82 (s, 3H), (m, 1H), (m, 2H), (m, 1H), 1.27 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 178.2, 160.0, 138.3, 138.2, 137.7, 135.4, 128.7, (2), 128.2, (2), 128.0, 127.9, 123.3, 114.6, 87.9, 86.8, 80.7, 77.9, 77.2, 76.0, 75.5, 75.3, 63.2, 55.4, 39.0, 27.4; HRMS (ESI) m/z calcd for C39H44O7SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-6-O-tert-butyldiphenylsilyl-1-thio-β-D-glucopyranoside (39). According to the general protocol A, (2,3,4-tri-O-benzyl-6-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl)trin-butylstannane 2 (144 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 39 (61.6 mg, 76%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2928, 2855, 1591, 1492, 1454, 1359, 1284, 1244, 1066, 907, 825, 735, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 2H), (m, 19H), (m, 2H), (m, 2H), (m, 4H), 4.75 (d, J = 10.4 Hz, 1H), 4.68 (d, J = 10.7 Hz, 1H), 4.55 (d, J = 9.7 Hz, 1H), (m, 2H), (m, 1H), 3.74 (s, 3H), 3.70 (t, J = 8.8 Hz, 1H), 3.48 (dd, J = 9.7, 8.4 Hz, 1H), 3.35 (ddd, J = 9.3, 3.6, 1.9 Hz, 1H), 1.09 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 159.7, 138.5, 138.4, 138.3, 136.0, 135.8, 135.0, 133.6, 133.2, (2), (3), 128.3, 128.1, 128.0, (3), 127.8, 124.1, 114.8, 114.6, 88.3, 87.1, 80.9, 80.0, 76.1, 75.4, 75.2, 62.9, 55.4, 27.0, 19.5; HRMS (ESI) m/z calcd for C50H54O6SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-6-O-(4-methoxybenzyl)-1-thio-β-D-glucopyranoside (40). According to the general protocol A, (2,3,4-tri-O-benzyl-6-O-(4-methoxybenzyl)-β-D-glucopyranosyl)tri-nbutylstannane S18 (127 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 40 (48.5 mg, 70%) as a white foam: = +3.1 (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2903, 1591, 1512, 1454, 1359, 1246, 1175, 1067, 828, 737, 698 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 15H), (m, 2H), (m, 2H), (m, 2H), 4.93 S13

14 (m, 4H), 4.74 (d, J = 10.3 Hz, 1H), (m, 3H), 4.47 (d, J = 11.5 Hz, 1H), 3.80 (s, 3H), 3.77 (s, 3H), (m, 3H), 3.61 (t, J = 9.2 Hz, 1H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.9, 159.3, 138.6, 138.3, 138.2, 135.3, 130.6, 129.5, (2), 128.5, 128.3, 128.1, 128.0, (2), 127.8, 123.7, 114.6, 113.9, 88.1, 86.9, 80.9, 79.2, 78.0, 75.9, 75.5, 75.1, 73.2, 68.9, 55.4 (2); HRMS (ESI) m/z calcd for C42H44O7SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-6-O-(2-naphthylmethyl)-1-thio-β-D-glucopyranoside (41). According to the general protocol A, [2,3,4-tri-O-benzyl-6-O-(2-naphthylmethyl)-β-D-glycopyranosyl]tri-nbutylstannane 2 (129.6 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 41 (69.1 mg, 97%) as a colorless oil: = -4.2 (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2862, 1591, 1492, 1454, 1358, 1284, 1244, 1063, 907, 817, 731, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 14H), (m, 6H), (m, 2H), (m, 7H), (m, 2H), (m, 4H), 3.56 (s, 3H), (m, 2H); 13 C NMR (75 MHz, CDCl3) δ 159.8, 138.5, 138.3, 138.1, 136.0, 135.2, 133.4, 133.1, 128.6, (2), 128.3, 128.2, 128.1, (2), (2), 127.8, 126.5, 126.2, (2), 123.6, 114.5, 88.0, 86.9, 80.9, 79.1, 78.0, 75.9, 75.5, 75.2, 73.7, 69.2, 55.2; HRMS (ESI) m/z calcd for C45H44O6SNa [M + Na] , found Methoxyphenyl 2-deoxy-3,4,6-tri-O-benzyl-1-thio-α-D-glucopyranoside (42). According to the general protocol B, (3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)tri-n-butylstannane 2 (141 mg, mmol), 1- ((4-methoxyphenyl)thio)pyrrolidine-2,5-dione S14 (23.7 mg, mmol), JackiePhos (44.0 mg, mmol), KF (17.4 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 42 (23.4 mg, 42%) as a colorless oil: = (c = 0.40, CHCl3); IR (ATR) ν = 3028, 2903, 1591, 1492, 1453, 1361, 1285, 1243, 1175, 1087, 1026, 827, 734, 696 cm - 1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), (m, 2H), (m, 2H), 5.51 (d, J = 5.7 Hz, 1H), 4.91 (d, J = 10.9 Hz, 1H), (m, 2H), 4.61 (d, J = 12.0 Hz, 1H), (m, 1H), 4.46 (d, J = 12.0 Hz, 1H), 4.37 (ddd, J = 9.8, 4.6, 2.0 Hz, 1H), 3.98 (ddd, J = 11.7, 8.7, 4.9 Hz, 1H), (m, 1H), 3.76 (s, 3H), 3.70 (dd, J = 10.6, 2.0 Hz, 1H), 3.60 (dd, J = 9.9, 8.7 Hz, 1H), 2.45 (ddd, J = 13.3, 4.9, 1.3 Hz, 1H), 2.08 (ddd, J = 13.4, 11.6, 5.7 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 159.7, 138.6, 138.6, 138.4, 134.7, 128.6, 128.5, 128.4, 128.1, 128.0, 127.9, 127.8, 127.8, 127.7, 114.7, 85.1, 78.8, 78.0, 75.1, 73.6, 72.0, 71.7, 69.3, 55.4, 36.2; HRMS (ESI) m/z calcd for C34H36O5SNa [M + Na] , found S14

15 4-Methoxyphenyl 2-deoxy-3,4,6-tri-O-benzyl-1-thio-α-D-galactopyranoside (43). According to the general protocol B, (3,4,6-tri-O-benzyl-2-deoxy-β-D-galactopyranosyl)tri-n-butylstannane S19 (141.4 mg, mmol), 1-((4-methoxyphenyl)thio)pyrrolidine-2,5-dione S14 (23.7 mg, mmol), JackiePhos (44.0 mg, mmol), KF (17.4 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4- dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 43 (29.0 mg, 52%) as a white foam: = (c = 13.3, CHCl3); IR (ATR) ν = 3029, 2865, 1596, 1495, 1458, 1365, 1286, 1249, 1093, 1063, 1029, 832, 739, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 17H), (m, 2H), 5.56 (d, J = 6.3 Hz, 1H), 4.95 (d, J = 11.6 Hz, 1H), (m, 3H), 4.47 (dd, J = 11.0, 5.7 Hz, 3H), (m, 2H), 3.74 (s, 3H), (m, 2H), 2.59 (ddd, J = 12.9, 11.7, 5.7 Hz, 1H), (m, 1H); 13 C NMR (75 MHz, CDCl3) δ 159.6, 139.0, 138.4, 138.4, 134.7, 128.6, 128.5, 128.4, 128.2, (2), 127.7, 127.6, 127.5, 125.1, 114.7, 114.6, 85.5, 75.5, 74.5, 73.6, 73.5, 70.9, 70.7, 69.9, 55.4, 31.8; HRMS (ESI) m/z calcd for C34H36O5SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-1-thio-β-L-fucopyranoside (44). According to the general protocol A, (2,3,4-tri-O-benzyl-β-L-fucopyranosyl)tri-n-butylstannane S20 (106 mg, mmol), 1,2-bis(4- methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 44 (29.5 mg, 53%) as a colorless oil: = -2.8 (c = 0.80, CHCl3); IR (ATR) ν = 3029, 2864, 1591, 1493, 1454, 1355, 1283, 1244, 1174, 1086, 1065, 909, 828, 730 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 15H), (m, 2H), 5.00 (d, J = 11.6 Hz, 1H), (m, 4H), 4.66 (d, J = 11.6 Hz, 1H), 4.49 (d, J = 9.6 Hz, 1H), 3.86 (t, J = 9.3 Hz, 1H), 3.76 (s, 3H), (m, 2H), (m, 1H), 1.26 (d, J = 6.4 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 159.5, 138.9, 138.7, 138.5, 134.8, 128.6, (2), 128.3, 128.0, 127.8, 127.7, 127.6, 124.4, 114.4, 88.3, 84.8, 77.3, 76.8, 75.7, 74.7, 73.0, 55.4, 17.4; HRMS (ESI) m/z calcd for C34H36O5SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-1-thio-β-L-quivonopyranoside (45). According to the general protocol A, (2,3,4-tri-O-benzyl-β-L-quivopyranosyl)tri-n-butylstannane S21 (106 mg, mmol), 1,2- bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 S15

16 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 45 (29.5 mg, 53%) as a colorless oil: = -8.1 (c = 0.80, CHCl3); IR (ATR) ν = 3030, 2898, 1591, 1492, 1453, 1358, 1284, 1244, 1173, 1065, 829, 735, 697 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 15H), (m, 2H), (m, 4H), 4.76 (d, J = 10.3 Hz, 1H), 4.65 (dd, J = 11.1, 2.3 Hz, 1H), 4.51 (d, J = 9.7 Hz, 1H), 3.81 (s, 3H), 3.66 (t, J = 8.9 Hz, 1H), (m, 2H), 3.20 (t, J = 9.2 Hz, 1H), 1.34 (d, J = 6.1 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 159.9, 138.6, 138.3, 138.2, 135.3, (2), 128.3, 128.1, (2), 127.8, 123.9, 114.6, 88.3, 86.8, 83.5, 81.4, 75.9, 75.7, 75.5 (2), 55.5, 18.3; HRMS (ESI) m/z calcd for C34H36O5SNa [M + Na] , found Methoxyphenyl 2,3,4-tri-O-benzyl-1-thio-β-D-arabinopyranoside (46). According to the general protocol A, (2,3,4-tri-O-benzyl-β-D-arabinosyl)tri-n-butylstannane 2 (104 mg, mmol), 1,2-bis(4- methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 8:1) 46 (45.0 mg, 83%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3029, 2863, 1591, 1493, 1453, 1356, 1284, 1244, 1083, 1026, 908, 827, 731 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 15H), (m, 2H), (m, 6H), 4.61 (d, J = 12.2 Hz, 1H), 4.27 (dd, J = 12.1, 5.5 Hz, 1H), 3.90 (t, J = 6.7 Hz, 1H), (m, 4H), 3.67 (dd, J = 7.1, 3.1 Hz, 1H), 3.42 (dd, J = 12.1, 2.4 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 159.6, 138.4, 138.3, 134.6, (2), 128.2, (2), 127.8, 127.1, 114.6, 88.3, 79.2, 77.4, 74.4, 72.6, 72.4, 71.2, 63.1, 55.4; HRMS (ESI) m/z calcd for C33H34O5SNa [M + Na] , found Methoxyphenyl 2,3,6-tri-O-benzyl-4-O-[2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl]-1-thio-β-Dglucopyranoside (47). According to the general protocol A, [2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl- (1 4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl]tri-n-butylstannane S22 (171 mg, mmol), 1,2-bis(4- methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 7:1) 47 (71.2 mg, 72%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2863, 1591, 1493, 1453, 1359, 1245, 1056, 1041, 908, 731, 695 cm -1 ; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 35H), (m, 2H), 5.58 (d, J = 3.7 Hz, 1H), (m, 4H), 4.72 (d, J = 10.6 Hz, 2H), (m, 7H), 4.37 (d, J = 10.8 Hz, 1H), 4.24 (d, J = 12.2 Hz, 1H), 4.02 (t, J = 9.3 Hz, 1H), (m, 2H), (m, 6H), 3.59 (dd, J = 10.1, 8.9 Hz, 1H), (m, 4H), 3.36 (dd, J = 10.7, 1.9 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 159.9, (2), 138.7, 138.5, (2), 135.4, (2), (4), 128.1, 128.0, 127.9, (2), (2), 127.6, 127.5, 127.3, 126.6, 123.4, 114.6, 97.2, 87.7, 86.9, 82.2, 81.0, 79.5, 78.8, 77.9, S16

17 75.6, 75.3, 75.1, 74.4, 73.6, 73.5, 73.4, 72.8, 71.2, 69.3, 68.4, 55.4; HRMS (ESI) m/z calcd for C68H70O11SNa [M + Na] , found Methoxyphenyl 2,3,6-tri-O-benzyl-4-O-[2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl]-1-thio-β-Dglucopyranoside (48). According to the general protocol A, [2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl- (1 4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl]tri-n-butylstannane 2 (171 mg, mmol), 1,2-bis(4- methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 6:1) 48 (65.2 mg, 66%) as a white foam: = -5.7 (c = 1.00, CHCl3); IR (ATR) ν = 3051, 3018, 2854, 1584, 1483, 1450, 1349, 1278, 1237, 1051, 906, 816, 727, 693 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 35H), (m, 2H), 5.10 (d, J = 10.5 Hz, 1H), 4.99 (d, J = 11.5 Hz, 1H), (m, 7H), (m, 6H), 4.25 (d, J = 11.8 Hz, 1H), (m, 8H), (m, 7H); 13 C NMR (75 MHz, CDCl3) δ 159.8, 139.2, 139.1, 138.9, 138.8, (2), 138.6, 138.2, 135.4, (3), (2), (2), 128.2, (2), 127.8, 127.7, (2), (2), 127.3, 123.5, 114.5, 103.0, 87.9, 85.2, 82.7, 80.1, 79.5, 76.6, 75.7, 75.5 (2), 74.9, 73.8, 73.5, 73.2, 72.8, 68.6, 68.2, 55.4; HRMS (ESI) m/z calcd for C68H70O11SNa [M + Na] , found Methoxyphenyl 3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-[2,3,4,6-tetra-O-benzyl-β-Dglucopyranosyl]-1-thio-β-D-glucopyranoside (49). According to the general protocol A, [2,3,4,6-tetra-Obenzyl-β-D-glucopyranosyl-(1 2)-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl]tri-nbutylstannane S23 (207 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (27.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 9:1) 49 (82.1 mg, 66%) as a colorless oil: = -2.5 (c = 1.00, CHCl3); IR (ATR) ν = 3378, 3028, 1492, 1452, 1264, 1176, 1072, 1016, 905, 731, 649, 599 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 2H), (m, 34H), (m, 2H), (m, 2H), (m, 3H), (m, 7H), (m, 3H), (m, 1H), (m, 3H), (m, 8H), (m, 2H), 3.36 (ddd, J = 11.2, 5.2, 2.9 Hz, 2H), 1.07 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 159.5, 138.9, 138.8, 138.7, 138.4, 138.3, 138.1, 136.0, 135.8, 135.1, 133.6, 133.2, (2), (2), (2), 128.4, (2), (2), (2), (2), 127.7, 127.6, 127.5, 124.8, 114.4, 102.4, 87.7, 87.2, 84.9, 82.9, 80.1, 78.1, 78.0, 75.9, 75.7, 75.6, 75.4, 75.3, 75.2, 75.1, 74.0, 68.9, 63.0, 55.4, 27.0, 19.4; HRMS (ESI) m/z calcd for C77H82O11SSiNa [M + Na] , found S17

18 Methyl 2,3,4-tri-O-benzyl-6-S-[2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl]-6-thio-α-Dglucopyranoside (51). 6 According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)trin-butylstannane 2 (122 mg, mmol), methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine-2,5-dione)-6-thio-α-Dglucopyranoside S24 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 51 (74.2 mg, 74%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2901, 1495, 1453, 1358, 1064, 907, 729 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 33H), (m, 2H), 5.00 (d, J = 10.9 Hz, 1H), (m, 8H), (m, 7H), (m, 1H), (m, 1H), (m, 4H), 3.53 (dd, J = 9.6, 3.6 Hz, 1H), (m, 6H), 3.11 (dd, J = 13.6, 2.5 Hz, 1H), 2.83 (dd, J = 13.6, 8.4 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 138.9, 138.7, 138.4, 138.3, (2), (2), (3), 128.4, 128.3, 128.2, 128.1, (2), (2), (2), (3), 97.9, 86.8, 85.8, 82.2, 82.1, 81.1, 80.1, 79.1, 78.0, 75.8, 75.6, 75.2, 75.1, 73.5, 73.4, 71.5, 69.1, 55.3, 32.3; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found Methyl 2,3,4-tri-O-benzyl-6-S-[2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl]-6-thio-α-Dglucopyranoside (52). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-Dgalactopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine- 2,5-dione)-6-thio-α-D-glucopyranoside S24 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 52 (88.3 mg, 88%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2906, 1495, 1453, 1359, 1207, 1087, 908, 732, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 35H), (m, 2H), (m, 11H), 4.49 (d, J = 9.6 Hz, 1H), (m, 2H), (m, 3H), 3.81 (t, J = 9.4 Hz, 1H), (m, 4H), (m, 2H), 3.33 (s, 3H), (m, 1H), (m, 1H); 13 C NMR (75 MHz, CDCl3) δ 138.9, 138.8, 138.5, 138.4, 138.3, 138.2, 138.0, (2), (3), 128.4, (2), (2), (2), (2), 127.9, (2), (2), 127.6, 127.6, 97.8, 85.9, 84.2, 82.1, 81.0, 80.2, 78.8, 77.1, 75.8, 75.8, 75.1, 74.6, 73.6, 73.4, 72.7, 71.1, 68.6, 55.3, 31.9; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found S18

19 Methyl 2,3,4-tri-O-benzyl-6-S-[2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1 4)-2,3,6-tri-O-benzyl-β- D-glucopyranosyl]-6-thio-α-D-glucopyranoside (53). According to the general protocol B, [2,3,4,6-tetra-Obenzyl-α-D-glucopyranosyl-(1 4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl]tri-n-butylstannane S22 (171 mg, mmol), methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine-2,5-dione)-6-thio-α-D-glucopyranoside S24 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 53 (91.6 mg, 75%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2903, 1495, 1453, 1359, 1207, 1137, 1045, 1045, 908, 731, 696 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 50H), 5.66 (d, J = 3.6 Hz, 1H), 5.00 (dd, J = 10.9, 1.5 Hz, 1H), (m, 9H), (m, 11H), 4.33 (d, J = 12.2 Hz, 1H), 4.10 (t, J = 9.2 Hz, 1H), (m, 18H), (m, 1H), (m, 1H); 13 C NMR (75 MHz, CDCl3) δ (2), 138.8, (2), 138.3, (2), 138.1, 138.0, (3), (3), (2), (2), (4), (2), (2), (2), (3), (2), 127.5, 127.2, 126.6, 97.9, 97.1, 86.7, 85.5, 82.2 (2), 82.1, 81.2, 80.1, 79.5, 78.8, 77.9, 75.9, 75.8, 75.4, 75.3, 75.1, 74.2, 73.6, 73.5, 73.4 (2), 72.9, 71.7, 71.2, 69.3, 68.4, 55.3, 32.1; HRMS (ESI) m/z calcd for C89H94O15SNa [M + Na] , found Methyl 2,3,4-tri-O-benzyl-6-S-[2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl]-6-thio-α-Dglucopyranoside (54). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)trin-butylstannane 2 (122 mg, mmol), methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine-2,5-dione)-6-thio-α-Dglucopyranoside S2 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 54 (86.3 mg, 86%) as a colorless oil: = (c = 1.00, CHCl3); IR (ATR) ν = 3499, 3030, 2902, 1495, 1453, 1359, 1312, 1206, 1069, 908, 731 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 33H), (m, 2H), 5.61 (d, J = 4.7 Hz, 1H), (m, 8H), (m, 5H), 4.50 (d, J = 10.9 Hz, 1H), 4.42 (d, J = 12.0 Hz, 1H), 4.20 (ddd, J = 10.0, 3.6, 2.0 Hz, 1H), 4.03 (t, J = 9.2 Hz, 1H), (m, 3H), (m, 5H), 3.41 (s, 3H), 3.01 (dd, J = 13.9, 2.7 Hz, 1H), 2.73 (dd, J = 13.8, 6.5 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ (2), 138.5, 138.3, 138.2, 138.0, 137.9, 128.6, (3), (2), 128.2, 128.1, (2), (2), (2), (2), 127.1, 98.1, 83.8, 82.5, 82.0, 80.4, 80.2, 79.4, 77.5, 75.8, 75.7, 75.4, 75.1, 73.5, 72.0, 70.7, 70.3, 68.7, 65.4, 55.4, 30.5; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found S19

20 Methyl 2,3,4-tri-O-benzyl-6-S-[3,4,6-tri-O-benzyl-2-deoxyl-α-D-glucopyranosyl]-6-thio-α-Dglucopyranoside (55). According to the general protocol B, (3,4,6-tri-O-benzyl-2-deoxy-β-Dglucopyranosyl)tri-n-butylstannane 2 (141.5 mg, mmol), methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine- 2,5-dione)-6-thio-α-D-glucopyranoside S24 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), KF (17.8 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 55 (54.7 mg, 61%) as a colorless oil: = (c = 7.15, CHCl3); IR (ATR) ν = 3033, 2906, 2869, 1499, 1458, 1365, 1327,1089, 1052, 914, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 30H), 5.48 (d, J = 5.4 Hz, 1H), 4.98 (d, J = 10.9 Hz, 1H), (m, 4H), (m, 6H), 4.51 (d, J = 11.0 Hz, 1H), 4.41 (d, J = 12.1 Hz, 1H), 4.09 (ddd, J = 9.8, 3.6, 2.0 Hz, 1H), (m, 3H), 3.76 (dd, J = 10.6, 3.6 Hz, 1H), (m, 7H), 3.00 (dd, J = 13.5, 2.9 Hz, 1H), (m, 1H), 2.30 (ddd, J = 13.5, 4.9, 1.3 Hz, 1H), 2.04 (ddd, J = 13.4, 11.5, 5.7 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 138.9, 138.7, 138.6, (2), 138.2, 98.1, 82.1, 81.0, 80.4, 80.2, 78.5, 78.1, 75.8, 75.3, 75.0, 73.6, 73.5, 72.0, 71.4, 69.8, 68.9, 55.4, 36.0, 32.2; HRMS (ESI) m/z calcd for C55H60O9SNa [M + Na] , found Methyl 2,3,6-tri-O-benzyl-4-S-[2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl]-4-thio-α-Dgalactopyranoside (56). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-Dglucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine-2,5- dione)-4-thio-α-d-galactopyranoside S25 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 56 (48.2 mg, 48%) as a colorless oil: = +9.1 (c = 0.90, CHCl3); IR (ATR) ν = 3028, 2862, 1495, 1452, 1355, 1207, 1088, 1027, 908, 843, 732, 695, 606, 462 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 33H), (m, 2H), 4.95 (d, J = 10.7 Hz, 1H), (m, 5H), (m, 2H), (m, 8H), 4.25 (ddd, J = 6.3, 4.4, 1.7 Hz, 1H), 4.07 (qd, J = 9.7, 3.5 Hz, 2H), (m, 2H), (m, 5H), 3.39 (d, J = 5.0 Hz, 4H), 3.29 (ddt, J = 9.6, 4.7, 2.9 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 138.9, 138.7, 138.7, 138.6, 138.3, 138.3, 128.5, 128.5, 128.5, 128.4, 128.3, 128.2, 128.1, (2), 127.9, (2), (2), 127.6, 127.5, 99.0, 86.4, 84.6, 82.8, 78.9 (2), 78.0, 75.8, 75.0, 74.9, 74.0, 73.5, 73.0, 72.2, 70.0, 69.4, 55.3, 47.9; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found S20

21 Methyl 2,3,6-tri-O-benzyl-4-S-[2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl]-4-thio-α-Dgalactopyranoside (57). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-α-Dmannopyranosyl)tri-n-butylstannane S15 (122 mg, mmol), methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine- 2,5-dione)-4-thio-α-D-galactopyranoside S25 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 57 (54.2 mg, 54%) as a colorless oil: = +5.7 (c =10.4, CHCl3); IR (ATR) ν = 3033, 2865, 1499, 1458, 1357, 1096, 1044, 910, 735, 689 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 33H), (m, 2H), 5.51 (d, J = 1.7 Hz, 1H), (m, 3H), (m, 10H), 4.46 (d, J = 10.7 Hz, 1H), 4.30 (d, J = 12.0 Hz, 1H), (m, 3H), (m, 2H), 3.89 (dd, J = 9.0, 3.0 Hz, 1H), 3.77 (dd, J = 9.8, 7.3 Hz, 1H), (m, 4H), 3.34 (s, 3H), 3.27 (dd, J = 11.1, 1.6 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 138.8, 138.6, 138.5, 138.4, 138.2, 137.8, 128.7, (2), (2), 128.3, 128.2, (2), 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.3, 127.1, 99.0, 83.9, 80.7, 77.7, 76.6, 76.1, 75.2, 74.7, 74.0, 73.8, 73.5, 72.6, 72.2, 71.9, 71.7, 69.8, 68.5, 68.2, 55.5, 50.6; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found Methyl 2,3,6-tri-O-benzyl-4-S-[2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl]-6-thio-α-Dglucopyranoside (58). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)trin-butylstannane 2 (122 mg, mmol), methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine-2,5-dione)-4-thio-α-Dglucopyranoside S26 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 58 (56.2 mg, 56%) as a colorless oil: = +2.3 (c = 21.8, CHCl3); IR (ATR) ν = 3033, 2899, 2866, 1499, 1458, 1361, 1048, 914, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 35H), (m, 8H), (m, 2H), (m, 4H), 4.44 (d, J = 1.8 Hz, 2H), 4.12 (dd, J = 10.7, 3.4 Hz, 1H), 4.02 (ddd, J = 11.1, 3.4, 1.8 Hz, 1H), 3.92 (dd, J = 10.6, 9.1 Hz, 1H), 3.71 (dd, J = 10.7, 1.8 Hz, 1H), (m, 5H), (m, 5H), 3.23 (t, J = 10.8 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 139.0, (2), (3), 138.2, (2), (2), 128.3, (2), 128.0, (3), 127.8, (2), (2), 127.5, 127.3, 98.5, 87.0, 84.1, 81.9, 81.1, 79.0, 77.9, 77.6, 75.9, 75.4, 75.0, 73.7, 73.5, 71.1, 69.5, 69.2, 55.3, 47.7; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found S21

22 Methyl 2,3,6-tri-O-benzyl-4-S-[2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl]-6-thio-α-Dglucopyranoside (59). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-α-Dgalactopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine- 2,5-dione)-4-thio-α-D-glucopyranoside S26 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 59 (61.2 mg, 61%) as a colorless oil: = +4.3 (c = 19.0, CHCl3); IR (ATR) ν = 3033, 2888, 2866, 1468, 1458, 1400, 1048, 915, 732, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 35H), (m, 2H), (m, 4H), (m, 6H), (m, 2H), 4.33 (q, J = 11.8 Hz, 2H), 4.07 (dd, J = 10.6, 3.7 Hz, 1H), (m, 5H), (m, 5H), 3.32 (s, 3H), 3.17 (t, J = 10.9 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 139.1, 138.9, (2), (2), 138.1, (2), 128.3, (3), 128.1, 128.0, (2), (2), 127.7, (2), (2), 127.3, 98.5, 85.2, 84.4, 81.2, 78.6, 77.9, 77.0, 76.0, 75.6, 74.7, 73.8, 73.6, 73.5, 73.2, 72.8, 71.4, 69.6, 68.8, 55.3, 48.0; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found Methyl 2,3,6-tri-benzyl-O-4-S-[2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl]-6-thio-α-Dglucopyranoside (60). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)trin-butylstannane 2 (122 mg, mmol), methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine-2,5-dione)-4-thio-α-Dglucopyranoside S26 (47.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 60 (55.2 mg, 55%) as a colorless oil: = +8.8 (c = 20.0, CHCl3); IR (ATR) ν = 3033, 2903, 2866, 1499, 1458, 1078, 1048, 914, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 7.38 (d, J = 4.4 Hz, 1H), 7.29 (ddt, J = 5.7, 4.4, 1.9 Hz, 26H), (m, 4H), 7.09 (ddt, J = 17.5, 7.6, 2.4 Hz, 4H), 6.02 (d, J = 5.0 Hz, 1H), 5.19 (d, J = 12.1 Hz, 1H), (m, 2H), (m, 4H), (m, 6H), 4.30 (d, J = 12.1 Hz, 1H), 4.18 (d, J = 11.9 Hz, 1H), (m, 2H), (m, 8H), 3.42 (s, 4H), 3.08 (td, J = 10.5, 5.1 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 139.2, 138.9, 138.5, 138.1, 138.0, 137.8, 128.7, (2), (3), 128.3, 128.2, 128.1(2), (2), 127.8, 127.7, (3), (2), 126.4, 98.3, 84.6, 82.5, 82.3, 81.2, 79.2, 77.3, 75.6, 75.4, 75.2, 73.7, 73.6, 73.2, 71.6, 71.5, 70.4, 68.4, 65.5, 55.5, 44.5; HRMS (ESI) m/z calcd for C62H66O10SNa [M + Na] , found S22

23 2,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl-2,3,4,6-tetra-O-acetyl-1-thio-β-glucopyranoside (61). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2,3,4,6-tetra-O-acetyl-1-S-(pyrrolidine-2,5-dione)-1-thio-β-D-glucopyranoside S27 (46.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 2:1) 61 ( 37.2 mg, 42%) as a colorless foam: = -1.3 (c = 6.05, CHCl3); IR (ATR) ν = 2929, 2865, 1752, 1458, 1368, 1216, 1037, 914, 739, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), (m, 3H), (m, 7H), (m, 3H), 4.13 (dd, J = 12.4, 4.6 Hz, 1H), 4.04 (dd, J = 12.3, 2.4 Hz, 1H), (m, 2H), (m, 2H), (m, 3H), 2.05 (s, 3H), 2.03 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 170.8, 170.4, 169.6, 169.5, 138.5, 138.2, 138.1, 137.8, (2), (2), (2), (2), (3), 86.8, 81.8, 81.7, 80.8, 79.4, 78.0, 75.9, 75.6, 75.2, 74.3, 73.5, 70.5, 69.0, 68.4, 62.1, 20.9, 20.9, 20.8, 20.7; HRMS (ESI) m/z calcd for C48H54O14SNa [M + Na] , found ,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl-2,3,4,6-tetra-O-benzoyl-1-thio-β-galactopyranoside (62). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2,3,4,6-tetra-O-benzoyl-S-(pyrrolidine-2,5-dione)-1-thio-β-D-glucopyranoside S28 (46.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 2:1) 62 ( 45.2 mg, 51%) as a colorless oil: = (c = 0.50, CHCl3); IR (ATR) ν = 3063, 2866, 1727, 1601, 1494, 1451, 1351, 1263, 1091, 907, 707, 594 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 7H), (m, 2H), (m, 1H), (m, 26H), (m, 4H), (m, 2H), 5.59 (dd, J = 9.9, 3.5 Hz, 1H), 5.28 (d, J = 10.1 Hz, 1H), (m, 5H), 4.67 (d, J = 10.6 Hz, 1H), (m, 4H), (m, 1H), (m, 1H), (m, 5H), (m, 1H); 13 C NMR (75 MHz, CDCl3) δ 166.0, 165.7, (2), 138.5, 138.3, 137.9, 133.7, (2), 130.2, 130.1, 129.9, 129.6, 129.4, 129.2, 129.0, (2), 128.7, 128.6, (3), (3), 128.1, 128.0, (2), 127.8, 86.8, 81.7, 81.3, 81.0, 79.4, 78.1, 75.9, 75.4, 75.2, 74.9, 73.6, 72.9, 69.1, 68.9, 68.7, 62.6; HRMS (ESI) m/z calcd for C68H62O14SNa [M + Na] , found S23

24 2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl-2,3,4,6-tetra-O-acetyl-1-thio-β-glucopyranoside (63). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)tri-n-butylstannane 2 (122 mg, mmol), 2,3,4,6-tetra-O-acetyl-1-S-(pyrrolidine-2,5-dione)-1-thio-β-D-glucopyranoside S27 (46.1 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 2:1) 63 ( 45.2 mg, 51%) as a colorless oil: = (c = 8.40, CHCl3); IR (ATR) ν = 2921, 2869, 1752, 1458, 1368, 1219, 1033, 914, 739, 702 cm - 1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), 5.77 (d, J = 4.8 Hz, 1H), (m, 3H), 4.91 (d, J = 10.9 Hz, 1H), (m, 6H), (m, 2H), (m, 2H), 4.02 (dd, J = 12.4, 2.2 Hz, 1H), (m, 6H), 2.03 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H), 2.00 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 170.7, 170.4, 169.4, 169.3, 138.7, 138.3, 138.0, 137.7, 128.6, (2), 128.2, (2), 128.0, (2), (2), 83.5, 82.6, 82.4, 79.2, 76.2, 75.8, 75.3, 74.3, 73.7, 72.0, 71.9, 71.3, 68.4, 68.0, 62.0, 20.9, 20.8 (2), 20.7; HRMS (ESI) m/z calcd for C48H54O14SNa [M + Na] , found Ethyl N-(tert-butoxycarbonyl)-S-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-L-cysteinate (64). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 (81.4 mg, mmol), (R)-ethyl 2-((tert-butoxycarbonyl)amino)-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate S29 (51.9 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 90 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 64 ( 40.1 mg, 52%) as a colorless foam: = -3.3 (c = 1.00, CHCl3); IR (ATR) ν = 3361, 3030, 2977, 2903, 1713, 1496, 1453, 1365, 1159, 1062, 735, 697 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), 5.86 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 2H), (m, 3H), 4.46 (d, J = 9.7 Hz, 1H), 4.19 (qd, J = 7.1, 1.2 Hz, 2H), (m, 4H), (m, 2H), 3.24 (dd, J = 14.2, 4.3 Hz, 1H), 3.12 (dd, J = 14.3, 5.9 Hz, 1H), 1.45 (s, 9H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 170.8, 155.5, 138.6, 138.2, 138.1, 137.9, (3), 128.4, (2), (2), (2), 86.7, 84.9, 81.4, 80.0, 79.2, 77.8, 75.8, 75.6, 75.2, 73.7, 69.0, 61.7, 54.1, 32.7, 28.5, 14.3; HRMS (ESI) m/z calcd for C44H53O9SNNa [M + Na] , found S24

25 Ethyl N-(tert-butoxycarbonyl)-S-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-L-cysteinate (65). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)tri-n-butylstannane 2 (81.4 mg, mmol), (R)-ethyl 2-((tert-butoxycarbonyl)amino)-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate S29 (51.9 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 90 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 65 (35.5 mg, 46%) as a colorless foam: = +5.8 (c = 8.00, CHCl3); IR (ATR) ν = 3342, 2925, 2869, 1718, 1499, 1458, 1163, 1074, 1029, 739, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 18H), (m, 2H), 5.77 (d, J = 8.8 Hz, 1H), 5.32 (d, J = 4.9 Hz, 1H), 4.93 (d, J = 10.8 Hz, 1H), (m, 2H), (m, 4H), (m, 2H), 4.19 (q, J = 7.2 Hz, 2H), 4.12 (dt, J = 9.5, 2.1 Hz, 1H), (m, 5H), 3.23 (dd, J = 14.2, 5.6 Hz, 1H), 2.86 (dd, J = 14.2, 4.2 Hz, 1H), 1.45 (s, 9H), 1.27 (t, J = 7.1 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 171.1, 155.6, 138.8, 138.3, 138.0, 137.8, 128.6, 128.5, 128.5, 128.2, 128.1, 128.1, 128.1, 128.0, 127.9, 127.8, 127.8, 85.4, 82.4, 80.1, 79.6, 78.1, 75.9, 75.3, 73.7, 72.6, 71.5, 68.6, 61.7, 53.9, 34.0, 28.5, 14.3; HRMS (ESI) m/z calcd for C44H53O9SNNa [M + Na] , found Ethyl N-(tert-butoxycarbonyl)-S-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(14)-2,3,6-tri-Obenzyl-β-D-glucopyranosyl)-L-cysteinate (66). According to the general protocol B, [2,3,4,6-tetra-Obenzyl-β-D-galactopyranosyl-(1 4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl]tri-n-butylstannane 2 (125 mg, mmol), (R)-ethyl 2-((tert-butoxycarbonyl)amino)-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate S29 (51.9 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 90 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 5:1) 66 ( 43.3 mg, 36%) as a colorless foam: = (c = 12.8, CHCl3); IR (ATR) ν = 3361, 3033, 2865, 1715, 1499, 1458, 1368, 1163, 1063, 914, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 35H), 5.86 (d, J = 8.0 Hz, 1H), 5.11 (d, J = 10.7 Hz, 1H), 4.98 (d, J = 11.5 Hz, 1H), (m, 7H), (m, 3H), (m, 3H), (m, 4H), 4.01 (t, J = 9.4 Hz, 1H), 3.93 (d, J = 2.9 Hz, 1H), 3.86 (dd, J = 10.9, 3.8 Hz, 1H), (m, 2H), 3.58 (t, J = 8.8 Hz, 1H), (m, 6H), (m, 1H), (m, 1H), 1.40 (s, 9H), 1.24 (t, J = 7.1 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 170.8, 155.5, (2), 138.9, 138.7, 138.4, 138.2, (3), (2), (2), 128.2, 128.1, 128.0, (2), (2), 127.7, (2), (2), 127.2, 102.9, 84.9, 84.7, 82.6, 80.6, 80.1, 79.5, 76.4, 75.6, 75.5, 75.4, 74.8, 73.8, 73.5, 73.3, 73.1, 72.7, 68.3, 68.0, 61.6, 54.1, 32.4, 28.4, 14.3; HRMS (ESI) m/z calcd for C71H81O14SNNa [M + Na] , found S25

26 tert-butyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-Lcysteinate (67). According to the general protocol B, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-nbutylstannane 2 (81.4 mg, mmol), (R)-tert-butyl 2-((S)-2-((tert-butoxycarbonyl)amino)-3- phenylpropanamido)-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate S30 (78.2 mg, mmol), JackiePhos (44.0 mg, mmol), and CuCl (5.00 mg, mmol) were added to anhydrous 1,4-dioxane (3.00 ml). The reaction mixture was heated under N2 at 90 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 3:1) 67 (56.8 mg, 60%) as a colorless foam: = +5.9 (c = 14.3, CHCl3); IR (ATR) ν = 3301, 2981, 2938, 1663, 1499, 1468, 1372, 1253, 1156, 1056, 914, 847, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 20H), 5.55 (s, 1H), (m, 10H), (m, 3H), (m, 1H), (m, 6H), 2.80 (dd, J = 13.9, 8.2 Hz, 1H), 1.37 (s, 9H), 1.35 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 172.0, 169.0, 155.8, 138.7, 138.3, 138.1, 137.9, 137.1, 136.7, 129.6, 129.4, 128.8, (2), 128.5, 128.4, 128.2, 128.1, (2), 127.7, 126.8, 86.4, 83.1, 82.7, 82.0, 80.1, 78.9, 78.0, 75.8, 75.7, 74.9, 73.5, 68.9, 55.5, 52.8, 38.6, 28.4, 28.1; HRMS (ESI) m/z calcd for C55H66O10SN2Na [M + Na] , found ((4-Methoxyphenyl)thio)tetrahydro-2H-pyran (71). According to the general protocol A, tri-nbutyl(tetrahydro-2h-pyran-2-yl)stannane 2 (75.0 mg, mmol), 1-((4-methoxyphenyl)thio)pyrrolidine- 2,5-dione S14 (23.7 mg, mmol), CuCl (1.00 mg, mmol), and KF (17.4 mg, mmol) in PhMe (2.00 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc, 99:1) 71 (12.5 mg, 56%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ 7.44 (d, J = 8.8 Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 5.01 (dd, J = 6.2, 3.7 Hz, 1H), (m, 1H), 3.79 (s, 3H), (m, 1H), (m, 8H). Characterization data matched the literature report. 7 2-((3,4-Dimethoxyphenyl)thio)tetrahydro-2H-pyran (72). According to the general protocol A, tri-nbutyl(tetrahydro-2h-pyran-2-yl)stannane 2 (75.0 mg, mmol), 1-((3,4-dimethoxyphenyl)thio)pyrrolidine- 2,5-dione S8 (26.7 mg, mmol), CuCl (1.00 mg, mmol), and KF (17.4 mg, mmol) in PhMe (2.00 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc, 19:1) 72 (13.6 mg, 54%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ (m, 2H), 6.80 (d, J = 6.8 Hz, 1H), (m, 1H), (m, 1H), 3.87 (s, 3H), 3.86 (s, 3H), S26

27 (m, 1H), (m, 1H), (m, 2H), (m, 3H); 13 C NMR (75 MHz, CDCl3) δ (2), 125.7, 125.4, 116.0, 111.4, 86.3, 64.9, 55.9 (2), 31.5, 25.5, 21.8; HRMS (ESI) calcd for C13H18O3SNa [M + Na] + : , found ((4-Methoxyphenyl)thio)tetrahydrofuran (73). According to the general protocol A, tri-nbutyl(tetrahydrofuran-2-yl)stannane 2 (72.2 mg, mmol), 1-((4-methoxyphenyl)thio)pyrrolidine-2,5- dione S14 (23.7 mg, mmol), CuCl (1.00 mg, mmol), and KF (17.4 mg, mmol) in PhMe (2.00 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc, 99:1) 73 (14.9 mg, 71%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ 7.46 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 5.47 (dd, J = 7.0, 3.6 Hz, 1H), (m, 2H), 3.79 (s, 3H), (m, 1H), (m, 3H).Characterization data matched the literature report. 3 2-((3,4-Dimethoxyphenyl)thio)tetrahydrofuran (74). According to the general protocol A, tri-nbutyl(tetrahydrofuran-2-yl)stannane 2 (72.2 mg, mmol), 1-((3,4-dimethoxyphenyl)thio)pyrrolidine-2,5- dione S8 (26.7 mg, mmol), CuCl (1.00 mg, mmol), and KF (17.4 mg, mmol) in PhMe (2.0 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc, 19:1) 74 (15.1 mg, 63%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ (m, 2H), 6.81 (d, J = 8.2 Hz, 1H), 5.51 (dd, J = 7.2, 3.9 Hz, 1H), (m, 1H), (m, 1H), 3.88 (s, 3H), 3.86 (s, 3H), (m, 1H), (m, 3H); 13 C NMR (75 MHz, CDCl3) δ (2), 126.0, 125.6, 116.1, 111.5, 88.2, 67.3, 55.9 (2), 32.5, 24.9; HRMS (ESI) calcd for C12H16O3SNa [M + Na] + : , found tert-butyl 2-((4-methoxyphenyl)thio)pyrrolidine-1-carboxylate (75). According to the general protocol A, tert-butyl 2-(tri-n-butylstannyl)pyrrolidine-1-carboxylate 8 (46.0 mg, mmol), 1,2-bis(4- methoxyphenyl)disulfane S4 (41.8 mg, mmol), CuCl (1.00 mg, mmol), and KF (17.4 mg, mmol) in PhMe (2.0 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc, 19:1) 75 (19.7 mg, 64%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ 7.42 (d, J = 9.4 Hz, 2H), (m, 2H), (m, 1H), 3.80 (s, 3H), 3.39 (s, 2H), (m, 4H), (m, 9H). Characterization data matched the literature report. 9 S27

28 Benzyl-4-((4-methoxyphenyl)thio)azetidin-2-one (76). According to the general protocol A, 1-benzyl-4-(trin-butylstannyl)azetidin-2-one S31 (45.0 mg, mmol), 1,2-bis(4-methoxyphenyl)disulfane S4 (55.7 mg, mmol), CuI (1.90 mg, mmol) and LiF (7.80 mg, mmol) in 1,4-dioxane (2.0 ml) were heated under N2 at 130 ºC for 96 h afforded after chromatographic purification on SiO2 (Hexanes/EtOAc 9:1) 76 (20.7 mg, 69%) as a colorless oil: 1 H NMR (300 MHz, CDCl3) δ (m, 5H), (m, 2H), (m, 2H), 4.73 (d, J = 15.1 Hz, 1H), 4.65 (dd, J = 4.9, 2.2 Hz, 1H), 4.12 (d, J = 15.1 Hz, 1H), 3.81 (s, 3H), 3.20 (ddd, J = 14.9, 4.9, 0.6 Hz, 1H), 2.78 (ddd, J = 14.9, 2.2, 1.0 Hz, 1H); 13 C NMR (75 MHz, CDCl3) δ 165.3, 160.6, 137.0, 135.5, 128.8, 128.5, 127.8, 119.7, 114.9, 58.3, 55.4, 44.2, 43.9; HRMS (ESI) calcd for C17H17NO2SNa [M + Na] + : , found ,2-Bis(4-fluorophenyl)disulfane (S1). 11 According to the general procedure C, NaBO3 H2O (600.0 mg, 6.00 mmol) was added to a stirring solution of 4-fluorobenzenethiol (320 μl, 3.00 mmol) in AcOH (7.50 ml) and H2O (3.00 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes) to afford S1 (299 mg, 78%) as a pale yellow oil: 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 4H); 13 C NMR (75 MHz, CDCl3) δ 164.4, 161.1, (2), 131.4, 131.3, 116.5, 116.2; 19 F NMR (282 MHz, CDCl3) δ (tt, J = 8.5, 5.1 Hz). Characterization data matched the literature report. 11 1,2-Bis(4-(tert-butyl)phenyl)disulfane (S2). 11 According to the general procedure C, NaBO3 H2O (9.60 g, 96.0 mmol) was added to a stirring solution of 4-(tert-butyl)benzenethiol (4.00 g, 24.0 mmol) in AcOH (15.0 ml) and H2O (10.0 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes) to afford S2 (3.20 g, 80%) as a white solid: 1 H NMR (300 MHz, CDCl3) δ 7.52 (dd, J = 8.6, 2.0 Hz, 4H), 7.39 (dd, J = 8.5, 1.7 Hz, 4H), 1.37 (s, 9H), 1.36 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 149.7, 149.3, 128.8, 124.0, 114.2, 111.5, 56.1, Characterization data matched the literature report. 11 S28

29 N,N'-(Disulfanediylbis(4,1-phenylene))diacetamide (S3). 12 According to the general procedure C, NaBO3 H2O (600 mg, 6.00 mmol) was added to a stirring solution of 4-acetamidobenzenethiol (1.00 g, 6.00 mmol) in AcOH (10.0 ml) and H2O (4.00 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes) to afford S3 (8.17 g, 82%) as a light yellow solid: 1 H NMR (300 MHz, (CD3)2SO) δ (s, 2H), (m, 4H), (m, 4H), 2.04 (s, 6H); 13 C NMR (75 MHz, (CD3)2SO) δ 168.5, 139.5, 130.1, 129.3, 119.7, Characterization data matched the literature report. 12 1,2-Bis(4-methoxyphenyl)disulfane (S4). 12 According to the general procedure C, NaBO3 H2O (600 mg, 6.00 mmol) was added to a stirring solution of 4-methoxybenzenethiol (370 μl, 3.00 mmol) in AcOH (7.50 ml) and H2O (3.00 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 50:1) to afford S4 (430 mg, 99%) as a pale yellow solid: 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 4H), 3.80 (s, 6H); 13 C NMR (75 MHz, CDCl3) δ 160.0, 132.7, 128.5, 114.7, Characterization data matched the literature report. 12 1,2-Bis(4-(trifluoromethoxy)phenyl)disulfane (S5). 13 According to the general procedure C, NaBO3 H2O (300 mg, 3.00 mmol) was added to a stirring solution of 4-(trifluoromethoxy)benzenethiol (291 mg, 1.50 mmol) in AcOH (5.00 ml) and H2O (2.00 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 100:1) to afford S5 (250 mg, 86%) as a pale yellow oil: 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 4H); 13 C NMR (75 MHz, CDCl3) δ 148.8, 135.3, 129.4, 122.2, 121.8, 118.8; 19 F NMR (282 MHz, CDCl3) δ Characterization data matched the literature report ((3-Methoxyphenyl)thio)pyrrolidine-2,5-dione (S6). 14 According to the general procedure D, to a flamedried round bottom flask was charged N-chlorosuccinimide (140 mg, 1.05 mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and 3-methoxybenzenethiol (140 mg, 1.00 mmol) in CH2Cl2 (1.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 S29

30 minutes followed by the addition of triethylamine (154 μl, 1.10 mmol) in CH2Cl2 (1.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2 and the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 4:1) to afford S6 (105 mg, 44%) as a white solid: 1 H NMR (300 MHz, CDCl3) δ (m, 1H), (m, 2H), 6.88 (ddd, J = 8.2, 2.6, 1.2 Hz, 1H), 3.79 (s, 3H), 2.83 (s, 4H); 13 C NMR (75 MHz, CDCl3) δ 176.4, 160.1, 135.1, 130.3, 124.1, 116.9, 116.1, 55.6, Characterization data matched the literature report. 14 1,2-Bis(3,5-dimethylphenyl)disulfane (S7). 15 According to the general procedure C, NaBO3 H2O (300 mg, 3.00 mmol) was added to a stirring solution of 3,5-dimethylbenzenethiol (207 mg, 1.50 mmol) in AcOH (5.00 ml) and H2O (2.00 ml). The reaction mixture was stirred for 4 h and concentrated in vacuo. The crude mixture was purified via flash chromatography on SiO2 (Hexanes) to afford S7 (150 mg, 73%) as a pale yellow oil: 1 H NMR (300 MHz, CDCl3) δ 7.13 (s, 4H), 6.86 (s, 2H), 2.29 (s, 12H); 13 C NMR (75 MHz, CDCl3) δ 138.9, 137.0, 129.1, 125.3, Characterization data matched the literature report ((3,4-Dimethoxyphenyl)thio)pyrrolidine-2,5-dione (S8). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (140 mg, 1.05 mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and 3,4-dimethoxybenzenethiol (170 mg, 1.00 mmol) in CH2Cl2 (1.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (154 μl, 1.10 mmol) in CH2Cl2 (1.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2 and the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 1:1) to afford S8 (219 mg, 82%) as a white solid: IR (ATR) ν = 3011, 2936, 2843, 1722, 1584, 1506, 1298, 1234, 1138, 1022, 754 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 7.43 (dd, J = 8.3, 2.1 Hz, 1H), 7.33 (d, J = 2.1 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 3.88 (s, 3H), 3.88 (s, 3H), 2.77 (s, 4H); 13 C NMR (75 MHz, CDCl3) δ 176.7, 151.6, 149.1, 129.4, 124.7, 118.2, 111.3, 56.3, 56.1, 28.7; HRMS (ESI) m/z calcd for C12H13NO4SNa [M + Na] , found ,2-Di(naphthalen-2-yl)disulfane (S9). 16 A modified procedure to the general procedure C, iodine (190 mg, 0.75 mmol) was added to a stirring solution of naphthalene-2-thiol (240 mg, 1.50 mmol) in MeOH (7.50 ml). The reaction mixture was stirred for 4 h and quenched with sat. Na2S2O3. The resulting solution was extracted S30

31 with CH2Cl2. The organic solution was dried with Na2SO4, filtered, and concentrated. The crude mixture was purified via flash chromatography on SiO2 (Hexanes) to afford S9 (200 mg, 84%) as a white solid: 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 4H), (m, 2H), 7.62 (dd, J = 8.7, 1.9 Hz, 2H), (m, 4H); 13 C NMR (75 MHz, CDCl3) δ 134.4, 133.6, 132.7, 129.1, 127.9, 127.6, 126.9, 126.7, 126.4, Characterization data matched the literature report (iso-Propylthio)isoindoline-1,3-dione (S10). To a flame-dried round bottom flask was charged 2- propanethiol (186 μl, 2.00 mmol) and triethylamine (13.6 μl, 0.10 mmol) in CH2Cl2 (4.00 ml) at 0 C under N2. SO2Cl2 (162 μl, 2.00 mmol) was added dropwise and the reaction was allowed to stir for 30 minutes. A solution of phthalimide (294 mg, 2.00 mmol) and triethylamine (351 μl, 2.50 mmol) in CH2Cl2 (2.00 ml) was added dropwise. The reaction was allowed to stir for an additional 1.5 h while warming up to room temperature. When the reaction is completed, the crude reaction mixture was washed with brine and water. The organic layer was collected, dried (Na2SO4), filtered, and concentrated. The crude solid was triturated with a 1:1 mixture of hexanes and ethyl acetate to afford S10 (320 mg, 73%) as a white solid: IR (ATR) ν = 3003, 2947, 2255, 1745, 1380, 1290, 1048, 724 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 2H), 3.46 (hept, J = 6.7 Hz, 1H), 1.26 (d, J = 6.7 Hz, 6H); 13 C NMR (75 MHz, CDCl3) δ 168.9, 134.7, 132.1, 124.0, 41.5, 21.1; HRMS (ESI) m/z calcd for C11H11NO2SNa [M + Na] , found tert-butyl-(2-((2,5-dioxopyrrolidin-1-yl)thio)ethyl)carbamate (S11). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (140 mg, 1.05 mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and 2-(Boc-amino)ethanethiol (169 μl, 1.00 mmol) in CH2Cl2 (1.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (154 μl, 1.10 mmol) in CH2Cl2 (1.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2 and the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:2) to afford S11 (185 mg, 68%) as a white solid: IR (ATR) ν = 3387, 2977, 2933, 1711, 1510, 1309, 1249, 1145, 758 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 5.45 (s, 1H), 3.23 (td, J = 6.5, 5.2 Hz, 2H), (m, 2H), 2.85 (s, 4H), 1.44 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 177.6, 155.9, 79.7, 38.9, 38.5, 28.8, 28.5; HRMS (ESI) m/z calcd for C11H18N2O4SNa [M + Na] , found S31

32 2-Ethylhexyl-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate (S12). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (280 mg, 2.10 mmol) and anhydrous CH2Cl2 (8.00 ml) under N2. The mixture was cooled to 0 C and 2-ethylhexyl-3-mercaptopropionate (292 μl, 2.00 mmol) in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (308 μl, 2.20 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:1) to afford S12 (450 mg, 71%) as a colorless oil: IR (ATR) ν = 2959, 2933, 2862, 1722, 1309, 1246, 1141, 653 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 3.97 (dt, J = 5.9, 2.1 Hz, 2H), (m, 2H), 2.81 (s, 4H), (m, 2H), (m, 1H), (m, 8H), (m, 6H); 13 C NMR (75 MHz, CDCl3) δ 177.3, 171.8, 67.6, 38.8, 35.0, 32.9, 30.4, 29.0, 28.8, 23.8, 23.1, 14.2, 11.1; HRMS (ESI) m/z calcd for C15H25NO4SNa [M + Na] , found (R)-2,8-Dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl trifluoromethanesulfonate (S13a). 17 To an oven-dried round-bottom flask was charged (+)-δ-tocopherol (1.60 g, 3.97 mmol, 1.00 equiv), CH2Cl2 (20.0 ml, M), and pyridine (480 μl, 5.96 mmol, 1.50 equiv). The reaction was cooled to 0 C and trifluoromethanesulfonic anhydride (800 μl, 4.77 mmol, 1.20 equiv) was added dropwise. The reaction was allowed to stir for 30 min. The mixture was quenched with H2O and extracted with CH2Cl2. The organic layers were combined, dried (Na2SO4), and concentrated. The crude mixture was purified by column chromatography on SiO2 (Hexanes) to yield S13a (2.03 g, 96%) as a colorless oil. Characterization data matched the literature report Ethylhexyl 3-(((R)-2,8-dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl)thio)propanoate (S13b). To an oven-dried sealed tube equipped was charged (R)-2,8-dimethyl-2-((4R,8R)-4,8,12- trimethyltridecyl)chroman-6-yl trifluoromethanesulfonate S13a (300 mg, mmol), Pd2(dba)3 (25.6 mg, mmol), and XantPhos (32.4 mg, mmol) under N2. 1,4-Dioxane (3.00 ml), 3-mercaptopropionic acid 2-ethylhexyl ester (140 μl, mmol, 1.10 equiv), and N,N-diisopropylethylamine (200 μl, 1.12 mmol, 2.00 equiv) were added and heated under N2 at 110 C for 20 h. After cooling to rt, the reaction mixture was filtered, concentrated, and directly purified by column chromatography on SiO2 (Hexanes:EtOAc, 1:0 then 99:1) to yield S13b (0.268 g, 79%) as a light yellow oil: = (c = 0.20, CHCl3); 1 H NMR (300 S32

33 MHz, CDCl3) δ 7.05 (s, 1H), 7.01 (s, 1H), (m, 2H), 3.03 (t, J = 7.4 Hz, 2H), (m, 2H), 2.58 (t, J = 7.4 Hz, 2H), 2.14 (s, 3H), (m, 2H), (m, 51H); 13 C NMR (75 MHz, CDCl3) δ 172.2, 152.1, 132.9, 131.6, 127.2, 122.7, 121.2, 76.4, 67.0, 40.2, 39.4, 38.8, 37.5, 37.4 (2), 37.3, 34.8 (2), 32.7, 31.3, 31.1, 30.4, 28.9, 28.0 (2), 24.5, 24.2, 23.8, 23.0, 22.7, 22.6, 22.2, 21.0, 19.8, 19.7, 16.0, 14.1, 11.0; HRMS (ESI) calcd for C38H66O3SNa [M + Na] , found (R)-2,8-Dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chromane-6-thiol (S13c). To an oven-dried roundbottom flask was charged 2-ethylhexyl 3-(((R)-2,8-dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6- yl)thio)propanoate S13b (257 mg, mmol) and absolute EtOH (8.60 ml, M). Sodium tert-butoxide (738 mg, 7.67 mmol) was added in one portion and stirred at rt for 0.5 h. The reaction mixture was quenched with sat. NH4Cl (aq) and extracted with CH2Cl2. The combined organic layers were dried (Na2SO4) and purified by column chromatography on SiO2 (Hexanes) to yield S13c (82.8 mg, 46%) as a colorless oil: = (c = 0.025, CHCl3); 1 H NMR (300 MHz, CDCl3) δ 6.95 (s, 1H), 6.92 (s, 1H), 3.27 (s, 1H), 2.70 (t, J = 6.8 Hz, 2H), 2.12 (s, 3H), (m, 2H), (m, 24H), (m, 12H); 13 C NMR (75 MHz, CDCl3) δ 151.2, 131.5, 129.8, 127.4, 121.4, 117.0, 76.2, 40.0, 39.4, 37.5, 37.4, 37.3, 32.8, 32.7, 31.1, 28.0, 24.8, 24.5, 24.2, 22.7, 22.6, 22.2, 20.9, 19.8, 19.7, 15.9; HRMS (ESI) calcd for C27H46OSNa [M + Na] , found (((R)-2,8-Dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl)thio)pyrrolidine-2,5-dione (S13). According to the general procedure D, to a flame-dried round bottom flask was charged N- chlorosuccinimide (100 mg, mmol) and anhydrous CH2Cl2 (0.750 ml) under N2. The mixture was cooled to 0 C and (R)-2,8-dimethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chromane-6-thiol S13c (300 mg, mmol) in CH2Cl2 (0.720 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (110 μl, mmol) in CH2Cl2 (0.790 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 4:1) to afford S13 (70.7 mg, 19%) as a light yellow oil: = (c = 0.08, CHCl3); 1 H NMR (300 MHz, CDCl3) δ 7.38 (s, 2H), (m, 6H), 2.10 (s, 3H), (m, 2H), (m, 24H), (m, 12H); 13 C NMR (75 MHz, CDCl3) δ 176.7, 154.9, 135.6, 134.9, 127.5, 122, 121.2, 77.2, 40.3, 39.4, 37.4 (2), 37.3, 32.8, 32.7, 30.7, 28.6, 28.0, 24.8, 24.4, 24.3, 22.7, 22.6, 22.0, 20.9, 19.8, 19.6, 15.9; HRMS (ESI) calcd for C31H49NO3SNa [M + Na] , found S33

34 1-((4-Methoxyphenyl)thio)pyrrolidine-2,5-dione (S14). 18 According to the general procedure D, to a flamedried round bottom flask was charged N-chlorosuccinimide (701 mg, 5.25 mmol) and anhydrous CH2Cl2 (5.25 ml) under N2. The mixture was cooled to 0 C and 4-methoxybenzenethiol (610 μl, 5.00 mmol) in CH2Cl2 (5.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (770 μl, 5.50 mmol) in CH2Cl2 (5.50 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:1) to afford S14 (0.969 g, 82%) as a white solid: 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 2H), 3.79 (s, 3H), 2.74 (s, 4H); 13 C NMR (75 MHz, CDCl3) δ 176.6, 161.9, 137.4, 124.6, 114.8, 55.5, 28.7; Characterization data matched the literature report. 18 (2,3,4,5-Tetra-O-benzyl-α-D-mannopyranosyl)tri-n-butylstannane (S15). To a flame-dried round bottom flask was charged 1,2-O-(1-methoxyethylidene)-3,4,6-tris-O-(phenylmethyl)-β-D-mannopyranose (14.0 g, 7.92 mmol) and anh. CH2Cl2 (80.0 ml) under N2. TMSCl (11.9 mmol, 11.9 ml) was then added and the mixture was refluxed for 1 h. When the reaction is complete, the solvent was removed in vacuo. The flask containing the crude material was purged three times with N2, dissolved in anh. THF (80.0 ml), and cooled down to -40 C. Potassium tert-butoxide (2.67 g, 23.8 mmol) was added and the reaction was allowed to stir for 30 mins. The reaction was poured into a 2:1 mixture of chloroform and brine (120 ml). The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried (Na2SO4), filtered, and concentrated. The crude material was purified via recrystallization (Hexanes/EtOAc). The mostly pure epoxide was charged to a flame-dried round bottom and purged three times with nitrogen. Dry THF was added (80.0 ml) and the mixture was cooled down to -40 C. MeMgSnBu3 was then added and the reaction was stirred for 2 h. Quench the reaction with H2O and filter through a pad of Celite. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried (Na2SO4), filtered, and concentrated. A short silica column was used to obtain a mostly pure product that was used directly in the next step. 400 mg of this material was dissolved in anh. THF (2.00 ml), cooled to 0 C, and KHMDS (1.66 ml, mmol, M in PhMe) was added. The reaction mixture was stirred at 0 C for 0.5 h, BnBr (130 μl, 1.10 mmol) was added, and the reaction was allowed to warm to rt and stirred for an additional 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 10:1) to afford S15 (415 mg, 71%) as a colorless oil: = +1.8 (c = 9.00, CHCl3); IR (ATR) ν = 3067, 3033, 2959, 2925, 2858, 1458, 1089, 739, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 18H), 4.97 (d, J = 11.2 Hz, 1H), (m, 2H), (m, 6H), 3.96 (t, J = 9.2 Hz, 1H), (m, 3H), 3.62 (dd, J = 9.1, 3.2 Hz, 1H), 3.22 (ddd, J = 9.3, 4.5, 2.8 Hz, 1H), (m, 6H), 1.26 (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 139.0, 138.7, 138.6, 138.5, (2), 128.4, (2), 128.0, (2), (2), 127.6, 127.5, 81.8, 80.0, 75.7, 75.1, 73.5, 72.7, 71.3, 70.1, 70.0, 29.1, 27.5, 13.8, 10.1; HRMS (ESI) m/z calcd for C46H62O5SnNa [M + Na] , found S34

35 (6-O-Acetyl-2,3,4-tri-O-benzyl-β-D-glycopyranosyl)tri-n-butylstannane (S16). To a solution of (2,3,4-tri- O-benzyl-β-D-glycopyranosyl)tri-n-butylstannane 2 (217 mg, mmol) was added acetic anhydride (1.00 ml) and pyridine (2.00 ml) at rt. The reaction was allowed to stir for 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 10:1) to afford S16 (220 mg, 96%) as a colorless oil: = (c = 9.50, CHCl3); IR (ATR) ν = 3067, 3033, 2959, 2925, 2873, 1745, 1238, 1056, 1033, 758 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 5.05 (d, J = 11.1 Hz, 1H), (m, 3H), (m, 2H), 4.32 (dd, J = 11.7, 2.1 Hz, 1H), 4.12 (dd, J = 11.7, 5.6 Hz, 1H), (m, 2H), (m, 2H), 3.34 (ddd, J = 9.7, 5.6, 2.1 Hz, 1H), 2.03 (s, 3H), (m, 6H), (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 170.9, (2), 138.0, (2), 128.4, 128.1, 128.0, (2), 127.6, 127.5, 89.6, 81.8, 80.6, 79.3, 75.6, 75.3, 74.6, 74.5, 64.0, 29.2, 27.5, 20.9, 13.8, 9.2; HRMS (ESI) m/z calcd for C41H58O6SnNa [M + Na] , found (2,3,4-Tri-O-benzyl-6-O-pivaloyl-β-D-glycopyranosyl)tri-n-butylstannane (S17). To a solution of (2,3,4- tri-o-benzyl-β-d-glycopyranosyl)tri-n-butylstannane 2 (217 mg, mmol) and triethylamine (150 μl, 1.05 mmol) in anhydrous CH2Cl2 (1.50 ml) under N2 at rt was added trimethylacetyl chloride (110 μl, mmol). The reaction was allowed to stir for 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 20:1) to afford S17 (205 mg, 85%) as a colorless oil: = (c = 3.50, CHCl3); IR (ATR) ν = 3067, 3033, 2959, 2925, 1733, 1097, 1059, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 5.07 (d, J = 11.1 Hz, 1H), (m, 3H), 4.65 (d, J = 11.2 Hz, 1H), 4.60 (d, J = 10.7 Hz, 1H), 4.40 (dd, J = 11.8, 2.0 Hz, 1H), 4.11 (dd, J = 11.8, 4.4 Hz, 1H), (m, 2H), (m, 2H), 3.33 (ddd, J = 9.6, 4.4, 2.0 Hz, 1H), 1.47 (m, 6H), (m, 15H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 178.3, 138.6, 138.5, 138.1, 128.7, 128.6, 128.4, (2), 127.9, 127.6, 127.4, 89.6, 81.9, 80.8, 79.3, 75.7, 75.4, 74.7, 74.5, 63.5, 39.0, 29.2, 27.5, 27.4, 13.8, 9.2; HRMS (ESI) m/z calcd for C44H64O6SnNa [M + Na] , found (2,3,4-Tri-O-benzyl-6-O-(4-methoxybenzyl)-β-D-glycopyranosyl)tri-n-butylstannane (S18). To a solution of (2,3,4-tri-O-benzyl-β-D-glycopyranosyl)tri-n-butylstannane 2 (217 mg, mmol) and TBAI (22.0 mg, mmol) in THF (1.50 ml) was added KHMDS (720 μl, M in PhMe) under N 2 at rt. After stirring for 1 h, PMB-Cl (81 μl, mmol) was added to the mixture and the reaction was allowed to stir for 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 20:1) to afford S18 (130 mg, 51%) as a colorless oil: = (c = 15.5, CHCl3); IR S35

36 (ATR) ν = 3067, 3033, 2955, 2921, 2854, 1517, 1458, 1249, 1059, 698 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 17H), (m, 2H), 5.07 (d, J = 11.2 Hz, 1H), 4.96 (d, J = 10.9 Hz, 1H), (m, 2H), 4.65 (d, J = 11.0 Hz, 2H), (m, 2H), 3.81 (s, 3H), (m, 5H), 3.53 (d, J = 10.8 Hz, 1H), (m, 1H), (m, 6H), (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 159.2, 138.8, 138.7, 138.6, 130.9, 129.3, 128.6, 128.5, 128.4, 128.0, (2), 127.7, (2), 113.8, 89.7, 83.4, 81.8, 79.4, 69.3, 55.4, 29.2, 27.6, 13.8, 9.3; HRMS (ESI) m/z calcd for C47H64O6SnNa [M + Na] , found (3,4,6-Tri-O-benzyl-2-deoxy-α-D-galactopyranosyl)tri-n-butylstannane (S19). To a flask containing 3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl chloride (434 mg, 1.00 mmol), anh. THF (7.00 ml) was added under N2 and cooled down to -78 C. A lithium naphthalenide (2.50 ml, 2.50 mmol, 1.00 M) was added dropwise over 5 min, followed immediately by tri-n-butyltin chloride (678 μl, 2.50 mmol) in one portion. The reaction mixture was allowed to stir at -78 C for 1 h. The reaction mixture was quenched with water and extracted with EtOAc. The organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 40:1) to afford S19 (210 mg, 30%) as a colorless oil: = +3.0 (c = 7.0, CHCl3); IR (ATR) ν = 3067, 3033, 2959, 2925, 2854, 1458, 1089, 739, 698 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 4.88 (d, J = 11.8 Hz, 1H), (m, 4H), (m, 2H), 3.84 (d, J = 2.4 Hz, 1H), (m, 4H), 2.53 (td, J = 12.8, 11.9, 5.6 Hz, 1H), (m, 1H), (m, 12H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 139.1, 138.8, 138.5, 128.6, 128.5, 128.3, 128.2, 127.8, (2), 127.6, 127.5, 77.7, 74.1, 73.8, 73.5, 70.4, 69.2, 29.3, 27.6, 13.8, 9.8; HRMS (ESI) m/z calcd for C39H56O4SnNa [M + Na] , found (2,3,4-Tri-O-benzyl-β-L-fucopyranosyl)tri-n-butylstannane (S20). (3,4-Di-O-benzyl-β-Lfucopyranosyl)tri-n-butylstannane 6 (617 mg, 1.00 mmol) was dissolved in anh. THF (2.00 ml), cooled to 0 C, and KHMDS (3.00 ml, 1.50 mmol, M in PhMe) was added. The reaction mixture was stirred at 0 C for 1 h. BnBr (238 μl, 2.00 mmol) was added and the reaction was allowed to warm to rt and stirred for an additional 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 50:1) to afford S20 (660 mg, 93%) as a colorless oil: = (c = 20.0, CHCl3); IR (ATR) ν = 3067, 3033, 2925, 2873, 2854, 1458, 1070, 735, 698 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 5.15 (d, J = 11.1 Hz, 1H), 5.04 (d, J = 11.8 Hz, 1H), 4.79 (d, J = 11.6 Hz, 1H), (m, 3H), (m, 1H), 3.73 (dd, J = 3.0, 1.2 Hz, 1H), 3.59 (dd, J = 8.9, 2.8 Hz, 1H), (m, 1H), 3.32 (qd, J = 6.4, 1.1 Hz, 1H), (m, 6H), 1.30 (m, 6H), 1.18 (d, J = 6.3 Hz, 3H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 139.3, 139.1, 138.6, 128.5, 128.3, 128.2, 127.8, (2), 127.4, 88.0, 78.3, 78.0, 77.3, 76.7, 75.2, 74.6 (2), 71.9, 29.2, 27.5, 17.5, 13.8, 9.3; HRMS (ESI) m/z calcd for C39H56O4SnNa [M + Na] , found S36

37 (2,3,4-Tri-O-benzyl-β-L-quinovopyranosyl)tri-n-butylstannane (S21). (3,4-Di-O-benzyl-β -Lquinovopyranosyl)tri-n-butylstannane 2 (750 mg, 1.21 mmol) was dissolved in anh. THF (6.00 ml), cooled to 0 C, and KHMDS (3.60 ml, 1.80 mmol, M in PhMe) was added. The reaction mixture was stirred at 0 C for 0.5 h. BnBr (285 ml, 2.40 mmol) was added and the reaction continued at 0 C for 0.5 h and rt for 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 20:1) to yield S21 (628 mg, 86%) as a pale yellow oil: = +7.8 (c = 1.00, CHCl3); IR (ATR) ν = 3030, 2922, 1487, 1453, 1363, 1209, 1069, 729, 689, 516 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 5.07 (d, J = 11.2 Hz, 1H), 4.95 (d, J = 10.9 Hz, 1H), 4.89 (d, J = 10.9 Hz, 1H), 4.84 (d, J = 11.0 Hz, 1H), (m, 3H), (m, 1H), 3.61 (t, J = 8.3 Hz, 1H), 3.51 (d, J = 11.0 Hz, 1H), (m, 1H), (m, 6H), (m, 9H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 138.8, 138.7, 138.5, 128.6, 128.4, 128.1, 127.9, 127.7, (2), 89.5, 85.2, 82.2, 79.3, 75.5, 75.5, 74.6, 74.4, 29.2, 27.5, 18.5, 13.8, 9.2; HRMS (ESI) m/z calcd for C39H56O4Na [M + Na] , found [2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl-(1 4)-3,6-di-O-benzyl-β-D-glucopyranosyl]tri-nbutylstannane (S22a). To a solution of hexa-o-benzyl maltal 19 (10.9 g, mmol) at 0 C, vigorously stirring biphasic solution of CH2Cl2 (20.0 ml), sat. NaHCO3 (500 ml), and acetone (20.0 ml), a solution of Oxone (18.0 g, 58.8 mmol) in H2O (75 ml) was added dropwise over 30 min. After the addition, the mixture was stirred for 0.5 h at 0 C, then for 2 h at rt. The crude reaction mixture was extracted with CH2Cl2. The combined organic phases were dried over Na2SO4 and concentrated to afford the epoxide as a white solid. The crude epoxide was dissolved in anh., degassed THF (30.0 ml) under N 2 and cooled to -45 C for the addition of MeMgSnBu3 (9.67 g, 29.4 mmol). The solution was warmed to -20 C and stirred for 2 h and quenched with H2O. The mixture was filtered through Celite and the organic phase was separated, the aqueous phase was extracted with CH2Cl2 and the combined organic layers were dried over Na2SO4 and concentrated. The crude material was purified by flash column chromatography on SiO2 (Hexanes:EtOAc, 20:1) to afford S22a ( 3.1 g, 20%) as a colorless oil: = +2.4 (c = 14.0, CHCl3); IR (ATR) ν = 3569, 3067, 3033, 2955, 2921, 2869, 1458, 1030, 735, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 28H), (m, 2H), 5.62 (d, J = 3.6 Hz, 1H), 5.06 (d, J = 11.9 Hz, 1H), 4.94 (d, J = 10.9 Hz, 1H), (m, 2H), (m, 3H), (m, 4H), 4.38 (d, J = 12.1 Hz, 1H), (m, 5H), (m, 3H), (m, 2H), (m, 3H), 3.37 (dq, J = 9.4, 1.9 Hz, 1H), 1.99 (d, J = 3.7 Hz, 1H), (m, 6H), (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 139.1, 139.0, 138.9, 138.6, 138.2, 138.1, 128.7, (2), 128.3, (2), 128.0, 127.9, (2), 127.6, 127.5, 127.4, 127.3, 97.3, 89.6, 83.3, 82.2, 79.9, 77.9, 75.7, 75.6, 75.1, 74.4, 74.1, 73.6, 73.5, 71.1, 69.7, 68.5, 29.2, 27.5, 13.9, 9.0; HRMS (ESI) m/z calcd for C66H84O10SnNa [M + Na] , found S37

38 [2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl-(1 4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl]tri-nbutylstannane (S22). [2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl-(1 4)-3,6-di-O-benzyl-β-Dglucopyranosyl]tri-n-butylstannane S22a (342 mg, mmol) was dissolved in anh. THF (1.50 ml), cooled to 0 C, and KHMDS (900 μl, mmol, 0.5 M in PhMe) was added. The reaction mixture was stirred at 0 C for 1 h. BnBr (71.0 μl, mmol) was added and the reaction was allowed to warm to rt and stirred for an additional 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 20:1) to afford S22 (320 mg, 87%) as a colorless oil: = +1.5 (c = 4.00, CHCl3); IR (ATR) ν = 3089, 3067, 2955, 2925, 2873, 1074, 1033, 754, 735 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 35H), 5.66 (d, J = 3.6 Hz, 1H), 5.02 (d, J = 11.8 Hz, 1H), (m, 5H), (m, 7H), 4.31 (d, J = 12.1 Hz, 1H), 4.10 (t, J = 8.9 Hz, 1H), (m, 11H), (m, 1H), (m, 6H), (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ (2), 138.7, 138.5, (2), (2), (2), 128.2, 128.0, 127.9, (2), 127.7, (2), (2), 127.4, 127.1, 126.6, 97.4, 89.6, 83.0, 82.3, 79.6, 78.0, 75.6, 75.1, 74.8, 74.3, 74.0, 73.9, 73.7, 73.6, 73.5, 71.0, 69.7, 68.5, 29.3, 27.6, 13.8, 9.3; HRMS (ESI) m/z calcd for C73H90O10SnNa [M + Na] , found [2,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl-(1 2)-3,4-di-O-benzyl-6-O-(tert-butyldiphenylsilyl)-β-Dglucopyranosyl]tri-n-butylstannane (S23). [3,4,6-Tri-O-benzyl-β-D-glucopyranosyl-(1 2)-3,4-di-Obenzyl-6-O-(tert-butyldiphenylsilyl)-β-D-glucopyranosyl]tri-n-butylstannane 2 (190 mg, mmol) was dissolved in anh. THF (1.00 ml), cooled to 0 C, and KHMDS (350 μl, mmol, 0.5 M in PhMe) was added. The reaction mixture was stirred at 0 C for 1 h. BnBr (26.0 μl, mmol) was added and the reaction was allowed to warm to rt and stirred for an additional 12 h. The crude mixture was concentrated with SiO2 and purified via flash chromatography on SiO2 (Hexanes:EtOAc, 30:1) to afford S23 (170 mg, 83%) as a colorless oil: = (c = 4.5, CHCl3); IR (ATR) ν = 3067, 3033, 2955, 2925, 2858, 1458, 1361, 1056, 735, 698 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 32H), (m, 4H), 5.12 (d, J = 7.9 Hz, 1H), 5.03 (d, J = 11.3 Hz, 1H), (m, 2H), (m, 6H), (m, 2H), 4.43 (d, J = 11.8 Hz, 1H), 4.19 (dd, J = 11.1, 8.5 Hz, 1H), (m, 6H), (m, 3H), (m, 2H), 3.17 (d, J = 9.3 Hz, 1H), (m, 6H), (m, 6H), (m, 15H), 0.85 (t, J = 7.3 Hz, 9H); 13 C NMR (75 MHz, CDCl3) δ 138.8, 138.7, 138.6, 138.5, (2), 136.0, 135.8, 133.1, (2), (2), 128.6, (2), (2), (2), 128.1, 128.0, (2), (2), 127.7, (2), 102.4, 90.2, 84.8, 84.1, 83.0, 78.6, 78.1, 77.4, 75.9, 75.6, 75.4, 75.3, 75.1, 74.5, 73.3, 69.0, 62.8, 31.1, 29.4, 27.8, 27.0, 19.4, 14.0, 9.5; HRMS (ESI) m/z calcd for C82H102O10SiSnNa [M + Na] , found S38

39 Methyl 2,3,4-tri-O-benzyl-6-S-(pyrrolidine-2,5-dione)-6-thio-α-D-glucopyranoside (S24). Methyl 6-Sacetyl-2,3,4-tri-O-benzyl-6-thio-α-D-glucopyranoside 20 (831 mg, 1.58 mmol) was dissolved in MeOH (7.50 ml) and sodium methoxide (100 μl, mmol, 25 wt % in MeOH) was added. The reaction was allowed to stir for 1 h and acidified with 1 M HCl (aq.). The crude reaction was washed twice with CH2Cl2 and the organic layers were collected, dried with Na2SO4, filtered, and concentrated. Then according to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (222 mg, 1.66 mmol) and anhydrous CH2Cl2 (6.00 ml) under N2. The mixture was cooled to 0 C and the crude thiol in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (245 μl, 1.74 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:2) to afford S24 (700 mg, 77%) as a white solid: = +5.6 (c = 3.50, CHCl3); IR (ATR) ν = 3067, 3033, 3014, 2929, 1730, 1152, 1074, 754 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 15H), 4.99 (d, J = 10.9 Hz, 1H), 4.93 (d, J = 11.1 Hz, 1H), (m, 2H), (m, 2H), 4.35 (d, J = 3.5 Hz, 1H), 3.97 (dd, J = 9.6, 8.8 Hz, 1H), 3.82 (ddd, J = 9.5, 6.7, 2.6 Hz, 1H), 3.62 (dd, J = 9.7, 8.7 Hz, 1H), 3.50 (dd, J = 9.7, 3.5 Hz, 1H), 3.40 (s, 3H), 3.31 (dd, J = 14.4, 2.6 Hz, 1H), 2.79 (dd, J = 14.4, 6.8 Hz, 1H), 2.65 (s, 4H); 13 C NMR (75 MHz, CDCl3) δ 176.8, 138.8, 138.3, (2), 128.5, 128.4, (3), 128.0, 127.8, 98.5, 81.9, 79.9, 79.8, 75.8, 75.2, 73.7, 70.4, 55.7, 39.3, 31.1, 28.7; HRMS (ESI) m/z calcd for C32H35NO7SNa [M + Na] , found Methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine-2,5-dione)-4-thio-α-D-galactopyranoside (S25). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (190 mg, 1.42 mmol) and anhydrous CH2Cl2 (6.00 ml) under N2. The mixture was cooled to 0 C and methyl 2,3,6-tri-Obenzyl-4-thio-α-D-glucopyranoside 9 (650 mg, 1.35 mmol) in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (210 μl, 1.49 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:1) to afford S25 (550 mg, 71%) as a white solid: = -1.1 (c = 7.0, CHCl3); IR (ATR) ν = 3067, 3014, 2910, 1726, 1305, 1152, 1044, 750 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 13H), 4.99 (d, J = 10.9 Hz, 1H), 4.93 S39

40 (d, J = 11.1 Hz, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 2H), 4.10 (dd, J = 9.9, 3.5 Hz, 1H), 3.83 (dd, J = 10.4, 5.4 Hz, 1H), 3.68 (dd, J = 10.4, 7.0 Hz, 1H), 3.37 (s, 3H), (m, 4H); 13 C NMR (75 MHz, CDCl3) δ 177.1, 138.6, 138.3, 138.1, (2), 128.5, 128.4, 128.2, 128.0, 127.9, 127.7, 99.4, 79.7, 77.1, 74.3, 74.1, 73.7, 70.2, 68.8, 55.5, 51.3, 28.5; HRMS (ESI) m/z calcd for C32H35NO7SNa [M + Na] , found Methyl 2,3,6-tri-O-benzyl-4-S-(pyrrolidine-2,5-dione)-4-thio-α-D-glucopyranoside (S26). Methyl 4-Sacetyl-2,3,6-tri-O-benzyl-4-thio-α-D-glucopyranoside 22 (850 mg, 2.05 mmol) was dissolved in MeOH (10.0 ml) and sodium methoxide (100 μl, mmol, 25 wt % in MeOH) was added. The reaction was allowed to stir for 1 h and acidified (ph 3)) with 1 M HCl (aq.). The crude reaction was washed twice with CH2Cl2 and the organic layers were collected, dried with Na2SO4, filtered, and concentrated. Then according to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (285 mg, 2.14 mmol) and anhydrous CH2Cl2 (6.00 ml) under N2. The mixture was cooled to 0 C and the crude thiol in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (316 μl, 2.25 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 3:1) to afford S26 (836 mg, 71%) as a white solid: = +1.9 (c = 5.0, CHCl3); IR (ATR) ν = 3067, 3029, 2906, 1730, 1134, 1093, 1048, 743, 702 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 13H), (m, 2H), 4.75 (d, J = 12.0 Hz, 1H), (m, 4H), 4.26 (dd, J = 11.2, 3.6 Hz, 1H), (m, 3H), 3.59 (dd, J = 9.0, 3.4 Hz, 1H), (m, 4H), (m, 4H). 13 C NMR (75 MHz, CDCl3) δ 177.3, 139.2, 138.4, 138.1, 128.6, (2), 128.3, (2), (2), 127.6, 98.2, 81.6, 77.3, 75.6, 73.7, 73.4, 69.9, 69.8, 55.6, 53.0, 28.6; HRMS (ESI) m/z calcd for C32H35NO7SNa [M + Na] , found ,3,4,6-Tetra-O-acetyl-1-S-(pyrrolidine-2,5-dione)-1-thio-β-D-glucopyranoside (S27). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (60.0 mg, mmol) and anhydrous CH2Cl2 (2.00 ml) under N2. The mixture was cooled to 0 C and 2,3,4,6-tetra-O-acetyl- 1-thio-β-D-glucopyranoside (155 mg, mmol) in CH2Cl2 (1.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (67.0 μl, mmol) in CH2Cl2 (1.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 1:1) to afford S27 (70.0 mg, 35%) as a white solid: = -11 (c = 4.5, CHCl3); IR (ATR) ν = 3026, 2959, 1745, 1372, 1212, 1037, 754 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 5.18 (t, J = 9.2 Hz, 1H), 5.05 (t, J = 9.7 Hz, 1H), 4.90 (dd, J = 10.1, 9.0 Hz, S40

41 1H), 4.68 (d, J = 10.1 Hz, 1H), 4.16 (qd, J = 12.4, 3.7 Hz, 2H), 3.65 (ddd, J = 10.0, 4.8, 2.7 Hz, 1H), 2.84 (s, 4H), 2.10 (s, 3H), 2.06 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H); 13 C NMR (75 MHz, CDCl3) δ 176.1, 170.7, 170.2, 170.0, 169.4, 86.4, 76.2, 73.8, 69.0, 68.0, 61.9, 28.7, 20.8, 20.7, 20.6; HRMS (ESI) m/z calcd for C18H23NO11SNa [M + Na] , found ,3,4,6-Tetra-O-benzoyl-S-(Pyrrolidine-2,5-dione)-1-thio-β-D-glucopyranoside (S28). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (105 mg, mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and 2,3,4,6-tetra-Obenzoyl-1-thio-β-D-glucopyranoside (490 mg, mmol) in CH2Cl2 (1.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (117 μl, mmol) in CH2Cl2 (1.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 1:1) to afford S28 (260 mg, 49%) as a white solid: = +5.9 (c = 5.0, CHCl3); IR (ATR) ν = 3070, 3018, 2957, 1730, 1268, 1097, 713 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 2H), (m, 4H), (m, 2H), (m, 1H), (m, 9H), 7.25 (m, 2H), 5.99 (dd, J = 3.3, 1.1 Hz, 1H), 5.74 (t, J = 9.9 Hz, 1H), 5.64 (dd, J = 9.9, 3.3 Hz, 1H), 5.17 (d, J = 10.0 Hz, 1H), 4.65 (dd, J = 11.3, 6.7 Hz, 1H), 4.39 (dd, J = 11.3, 6.3 Hz, 1H), (m, 1H), 2.74 (s, 4H); 13 C NMR (75 MHz, CDCl3) δ 176.1, 166.1, 165.9, 165.6, 165.5, 133.9, 133.7, 133.5, 130.2, 130.1, 129.9, 129.5, (2), (2), (2), 128.5, 86.9, 75.4, 72.6, 68.1, 67.3, 62.1, 28.7; HRMS (ESI) m/z calcd for C38H31NO11SNa [M + Na] , found (R)-Ethyl 2-((tert-butoxycarbonyl)amino)-3-((2,5-dioxopyrrolidin-1-yl)thio)propanoate (S29). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (280 mg, 2.10 mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and N-Boc- L-cysteine ethyl ester (500 mg, 2.00 mmol) in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (309 μl, 2.20 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 1:1) to afford S30 (260 mg, 84%) as a white solid: = -8.7 (c = 0.40, CHCl3); IR (ATR) ν = 3298, 2985, 1692, 1374, 1160, 1026, 754 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ 5.77 (d, J = 8.5 Hz, 1H), 4.55 (s, 1H), 4.15 (q, J = 7.4 Hz, 2H), (m, 1H), 3.01 (dd, J = 15.1, 5.6 Hz, 1H), 2.78 (s, 4H), 1.43 (s, 9H), 1.27 (t, J = 7.1 Hz, 3H); 13 C NMR (75 MHz, CDCl3) δ 177.2, 80.4, 62.2, 52.7, 39.5, 28.7, 28.5, 14.2; HRMS (ESI) m/z calcd for C14H22N2O6SNa [M + Na] , found S41

42 (R)-tert-Butyl 2-((S)-2-((tert-butoxycarbonyl)amino)-3-phenylpropanamido)-3-((2,5-dioxopyrrolidin-1- yl)thio)propanoate (S30). According to the general procedure D, to a flame-dried round bottom flask was charged N-chlorosuccinimide (280 mg, 2.10 mmol) and anhydrous CH2Cl2 (4.00 ml) under N2. The mixture was cooled to 0 C and Boc-L-cysteine ethyl ester (500 mg, 2.00 mmol) in CH2Cl2 (2.00 ml) was added dropwise via syringe pump over 20 minutes. The resulting mixture was stirred for 30 minutes followed by the addition of triethylamine (309 μl, 2.20 mmol) in CH2Cl2 (2.00 ml) via syringe pump over 20 minutes. The solution was allowed to stir for an additional 30 minutes and then quenched with water. The aqueous layer was washed twice with CH2Cl2, the organic layers were collected, dried with Na2SO4, filtered, and concentrated. The crude material was purified via flash chromatography on SiO2 (Hexanes:EtOAc, 1:1) to afford S30 (260 mg, 84%) as a white solid: = (c = 5.0, CHCl3); IR (ATR) ν = 3351, 3007, 2981, 2936, 1722, 1678, 1499, 1149, 754 cm -1 ; 1 H NMR (300 MHz, CDCl3) δ (m, 5H), 5.02 (d, J = 8.3 Hz, 1H), 4.79 (s, 1H), 4.35 (td, J = 8.2, 5.4 Hz, 1H), 3.56 (dd, J = 15.2, 3.0 Hz, 1H), 3.16 (dd, J = 14.0, 5.4 Hz, 1H), 2.97 (dd, J = 14.0, 8.2 Hz, 1H), 2.87 (dd, J = 15.2, 5.3 Hz, 1H), 2.80 (s, 4H), 1.45 (s, 9H), 1.36 (s, 9H); 13 C NMR (75 MHz, CDCl3) δ 177.8, 171.5, 168.9, 155.5, 136.6, 129.5, 128.7, 127.0, 83.3, 79.9, 55.8, 51.5, 40.7, 38.6, 28.8, 28.4, 28.0; HRMS (ESI) m/z calcd for C25H35N3NaO7SNa [M + Na] , found Benzyl-4-(tri-n-butylstannyl)azetidin-2-one (S31). A solution of 4-(tri-n-butylstannyl)azetidin-2-one 23 (0.700 g, 1.94 mmol) in anhydrous THF (9.70 ml) was cooled to 0 C, and a solution of KHMDS (4.27 ml, 2.14 mmol, 0.5 M in PhMe) was added. The solution was stirred at 0 C for 0.5 h, benzyl bromide (0.431 g, 2.52 mmol) was added, and the resulting solution was stirred for additional 0.5 h at 0 C and then for 6 h at rt. The reaction mixture was concentrated and directly purified by column chromatography on SiO2 (Hexanes:EtOAc, 1:0 then 85:15) to yield S31 (0.750 g, 86%) as a light yellow oil: 1 H NMR (300 MHz, CDCl3) δ (m, 5H), 4.80 (d, J = 15.4 Hz, 1H), 3.83 (d, J = 15.4 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 6H), (m, 6H), (m, 15H); 13 C NMR (75 MHz, CDCl3) δ 167.3, 136.0, 128.7, 128.0, 127.6, 46.7, 41.2, 40.4, 29.2, 29.1, 28.9, 27.8, 27.7, 27.4, 27.0 (2), 13.6, 8.9; HRMS (ESI) calcd for C22H37NOSnNa [M + Na] + : , found S42

43 Phenyl-1-thio-β-D-glucopyranoside. 10 Under N2, phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-Dglucopyranoside 10 (101.2 mg, mmol), anh. CH2Cl2 (1.60 ml) and mesitylene (0.265 ml, 1.91 mmol) were successively added into a flame dried glassware. The mixture was cooled to -78 C and BCl3 (1.27 ml, 1.27 mmol, 1.0 M in CH2Cl2) was added drop-wise over 5 min. The resulting solution was stirred at -78 C for 0.5 h, quenched by drop-wise addition of MeOH (2.0 ml) at -78 C, and allowed to stir for an additional 20 min. The resulting mixture was concentrated and directly purified by column chromatography on SiO2 (CH2Cl2:MeOH, 9:1) to afford glucopyranoside (42.2 mg, 72%) as a colorless oil: 1 H NMR (300 MHz, CD3OD) δ 7.55 (d, J = 7.2 Hz, 2H), 7.27 (qd, J = 9.9, 8.1, 4.4 Hz, 3H), 4.60 (dd, J = 9.7, 3.8 Hz, 1H), 3.86 (d, J = 12.0 Hz, 1H), 3.66 (dd, J = 12.1, 4.7 Hz, 1H), (m, 4H); 13 C NMR (75 MHz, CD3OD) δ 135.2, 132.7, (2), 128.3, 128.3, 89.4, 82.0, 79.6, 79.5, 73.7, 71.3, 62.8, Characterization data matched the literature report. 10 Phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside (10). 1 According to the general protocol A, (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)tri-n-butylstannane 2 8 (122 mg, mmol), or 1- (phenylthio)pyrrolidine-2,5-dione 9a (20.7 mg, mmol) or 1,2-diphenyldisulfane 9b (21.8 mg, mmol), and CuCl (30.0 mg, mmol) were added to anhydrous m-xylene and 1,2-dichloroethane (2:1, 3.00 ml). The reaction mixture was heated under N2 at 130 ºC for 96 h and afforded after chromatographic purification on SiO2 (Hexanes:EtOAc, 10:1) 10 without effect on the reaction yield and stereospecificity. S43

44 All DFT calculations were performed with the Gaussian 16 software package. 23 Geometry optimizations of all the minima and transition states were carried out at the B3LYP 24 level of theory with additional Grimme s D3 dispersion correction (Becke-Johnson damping) 25 using the def2-svp basis set. 26 Vibrational frequencies were computed at the same level to evaluate its zero-point vibrational energy (ZPVE) and thermal corrections at 298 K, as well as to check whether each optimized structure is a transition state or not. The single-point energies were computed at the same level of theory, combined with def2-tzvpp 27 basis set and SMD solvation model 28 for 1,4-dioxane using the optimized structures. The 3D diagrams of molecules were generated using CYLView. 29 In addition, to correct the Gibbs free energies under pressure of 1 atm to the standard state in solution (1 mol/l), a correction of RTln(cs/cg) (about 1.9 kcal/mol) is added to energies of all species. cs is the standard molar concentration in solution (1 mol/l), cg is the standard molar concentration in gas phase ( mol/l), and R is the gas constant. S44

45 S45

46 S46

47 S47

48 S48

49 S49

50 S50

51 S51

52 S52

53 S53

54 S54

55 S55

56 S56

57 S57

58 S58

59 S59

60 S60

61 S61

62 S62

63 S63

64 S64

65 S65

66 S66

67 S67

68 S68

69 S69

70 S70

71 S71

72 S72

73 S73

74 S74

75 S75

76 S76

77 S77

78 S78

79 S79

80 S80

81 S81

82 S82

83 S83

84 S84

85 S85

86 S86

87 S87

88 S88

89 S89

90 S90

91 S91

92 S92

93 S93

94 S94

95 S95

96 S96

97 S97

98 S98

99 S99

100 S100

101 S101

102 S102

103 S103

104 S104

105 S105

106 S106

107 S107

108 S108

109 S109

110 S110

111 S111

112 S112

113 S113

114 S114

115 S115

116 S116

117 S117

118 S118

119 S119

120 1. Dinkelaar, J.; de Jong, A. R.; van Meer, R.; Somers, M.; Lodder, G.; Overkleeft, H. S.; Codée, J. D.; van der Marel G. A. J. Org. Chem., 2009, 74, Zhu, F.; Rourke, M. J.; Yang, T.; Rodriguez, J.; Walczak, M. A. J. Am. Chem. Soc., 2016, 138, Li, X.; Huang, L.; Hu, X.; Huang, X. Org. Biomol. Chem., 2009, 7, Veleti, S. K.; Lindenberger, J. J.; Thanna, S.; Ronning, D. R.; Sucheck, S. J. J. Org. Chem., 2014, 79, Griffin, F. K.; Paterson, D. E.; Murphy, P. V.; Taylor, R. Eur. J. Org. Chem., 2002, 7, Kumar, A.; Schmidt, R. R. Eur. J. Org. Chem., 2012, 14, Schneider, C. C.; Manarin, F.; Panatieri, R. B.; Barros, O. S. R.; Zeni, G. J. Braz. Chem. Soc., 2010, 21, Rayner, P. J.; Gelardi, G.; O Brien, P.; Horan, R. A. J.; Blakemore, D. C. Org. Biomol. Chem., 2014, 12, Jin, Y.; Yang, H.; Fu, H. Chem. Commun., 2016, 52, Nielsen, M. M.; Stougaard, B. A.; Bols, M.; Glibstrup, E.; Pedersen, C. M. Eur. J. Org. Chem., 2017, 9, Shi, Y.; Chen, S.; Zhang, F; Chen, B. ChemistrySelect, 2018, 3, Zhu, R.; Shi, X. Synth. Comm., 2012, 42, Balgotra, S.; Verma, P.; Kour, J.; Gupta, S.; Vishwakarma, R.; Sawant, S. ChemistrySelect, 2018, 3, Savarin, C.; Srogl, J.; Liebeskind, L. S. Org. Lett., 2002, 4, Spurg, A.; Schnakenburg, G.; Waldvogel, S. R. Chem. Eur. J., 2009, 15, Maity, S.; Karmakar, U.; Samanta, R. Chem. Comm., 2017, 53, Furuya, T.; Strom, A. E.; Ritter, T. J. Am. Chem. Soc., 2009, 131, Hostier, T.; Ferey, V.; Ricci, G.; Pardo, D. G.; Cossy, J. Org. Lett., 2015, 17, Vedachalam, S.; Tan, S. M.; Teo, H. P.; Cai, S.; Liu, X. Org. Lett., 2012, 14, Weng, S.; Lin, Y.; Chen, C. Org. Lett., 2006, 8, Elhalabi, J.; Rice, K. G. Carbohydr. Res., 2001, 335, Ek, M.; Garegg, P. J.; Hultberg, H.; Oscarson, S. J. Carbohydr. Chem., 1983, 2, Nativi, C.; Ricci, A.; Taddei, M. Tetrahedron Lett., 1990, 31, Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, (a) Becke, A. D. J. Chem. Phys. 1993, 98, (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys., 1988, 37, Grimme, S.; Ehrlich, S.; Goerigk, L. J. Comp. Chem., 2011, 32, Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys., 2005, 7, Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, CYLview, 1.0b, C. Y. Legault, Université de Sherbrooke, 2009 ( S120

121 S121

122 S122

123 S123

124 S124

125 S125

126 S126

127 S127

128 S128

129 S129

130 S130

131 S131

132 S132

133 S133

134 S134

135 S135

136 S136

137 S137

138 S138

139 S139

140 S140

141 S141

142 S142

143 S143

144 S144

145 S145

146 S146

147 S147

148 S148

149 S149

150 S150

151 S151

152 S152

153 S153

154 S154

155 S155

156 S156

157 S157

158 S158

159 S159

160 S160

161 S161

162 S162

163 S163

164 S164

165 S165

166 S166

167 S167

168 S168

169 S169

170 S170

171 S171

172 S172

173 S173

174 S174

175 S175

176 S176

177 S177

178 S178

179 S179

180 S180

181 S181

182 S182

183 S183

184 S184

185 S185

186 S186

187 S187

188 S188

189 S189

190 S190

191 S191

192 S192

193 S193

194 S194

195 S195

196 S196

197 S197

198 S198

199 S199

200 S200

201 S201

202 S202

203 S203

204 S204

205 S205

206 S206

207 S207

208 S208

209 S209

210 S210

211 S211

212 S212

213 S213

214 S214

215 S215

216 S216

217 S217

218 S218

219 S219

220 S220

221 S221

222 S222

223 S223

224 S224

225 S225

226 S226

227 S227

228 S228

229 S229

230 S230

231 S231

232 S232

233 S233

234 S234

235 S235

236 S236

237 S237

238 S238

239 S239

240 S240

241 S241

242 S242

243 S243

244 S244

245 S245

246 S246

247 S247

248 S248

249 S249

250 S250

251 S251

252 S252

253 S253

254 S254

255 S255

256 S256

257 S257

258 S258

259 S259

260 S260

261 S261

262 S262

263 S263

264 S264

265 S265

266 S266

267 S267

268 S268

269 S269

270 S270

271 S271

272 S272

273 S273

274 S274

275 S275

276 S276

277 S277

278 S278

279 S279

280 S280

281 S281

282 S282

283 S283

284 S284

285 S285

286 S286

287 S287

288 S288

289 S289

290 S290

291 S291

292 S292

293 S293

294 S294

295 S295

296 S296

297 S297

298 S298

299 S299

300 S300

301 S301

302 S302

303 S303

304 S304

305 S305

306 S306

307 S307

308 S308

309 S309

310 S310

311 S311

312 S312

313 S313

314 S314

315 S315

316 S316

317 S317

318 S318

319 S319

320 S320

321 S321

322 S322

323 S323

324 S324

325 S325

326 S326

327 S327

328 S328

329 S329

330 S330

331 S331

332 S332

333 S333

334 S334

335 S335

336 S336

337 S337

338 S338

339 S339

340 S340

341 S341

342 S342

343 S343

344 S344

345 S345

346 S346

347 S347

348 S348

349 S349

350 S350

351 S351

352 S352

353 S353

354 S354

355 S355

356 S356

357 S357

358 S358

359 S359

360 S360

361 S361

362 S362

363 S363

364 S364

365 S365

366 S366

367 S367

368 S368

369 S369

370 S370

371 S371

372 S372

373 S373

374 S374

375 S375

376 S376

377 S377

378 S378

379 S379

380 S380

381 S381

382 S382

383 S383

384 S384

385 S385

386 S386

387 S387

388 S388

389 S389

390 S390

391 S391

392 S392

393 S393

394 S394

395 S395

396 S396

397 S397

398 S398

399 S399

400 S400

401 S401

402 S402

403 S403

404 S404

405 S405

406 S406

407 S407

408 S408

409 S409

410 S410

411 S411