1. General Information Unless otherwise noted, all reagents, catalysts and solvents were purchased from commercial suppliers and used without further

Supporting Information for Transformation of Alkynes into Chiral Alcohols via TfOH-Catalyzed Hydration and Ru-Catalyzed Tandem Asymmetric Hydrogenation Sensheng Liu, Huan Liu, Haifeng Zhou, *,, Qixing Liu, and Jinliang Lv *, Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, China Yichang Humanwell Pharmaceutical Co., Ltd, Yichang, 443005, China 1. General Information..S2 2. Optimization of the Hydration Step.. S2 3. General Procedure for the Synthesis of Racemic Aryl Alcohols......S2 4. Reaction Conditions for the Tandem Reactions....S2 5. General Procedure for the Hydration and Asymmetric Hydrogenation of Aryl Alkynes... S4 6. General Procedure for the Hydration and Asymmetric Hydrogenation of 1,3-diethynylbenzene....... S4 7. General Procedure for the Hydration and Asymmetric Hydrogenation of 1,4-diethynylbenzene...... S4 8. General Procedure for the Hydration and Asymmetric Hydrogenation of 1,3,5-triethynylbenzene.....S5 9. General Procedure for Gram Scale Reaction S5 10. Analytical Data of the Products S6 11. 1 H NMR and 13 C NMR Spectra of the Products...S12 12. HPLC Spectra of Products....S33 1

1. General Information Unless otherwise noted, all reagents, catalysts and solvents were purchased from commercial suppliers and used without further purification. Column Chromatography was performed with silica gel (200-300 mesh). NMR spectra were recorded on Bruker ADVANCE III (400 MHz) spectrometers. CDCl 3 was used for the NMR analysis with tetramethylsilane as the internal standard. Chemical shifts were reported up field to TMS ( ppm) for 1 H NMR and relative to CDCl 3 (77.0 ppm) for 13 C NMR. HPLC analysis was conducted on a Waters 2489 Series instrument with chiral column OJ-H, AD-H, AS-H and OD-H. Optical rotations were measured on a MCP-500. Melting points were determined using X-4 made by Peking Taike Apparatus Co., Ltd. HRMS spectra were acquired using an Agilent 6210 ESI/TOF mass spectrometer. 2. Optimization of the Hydration Step a entry T/ t/h yield (%) 1 b 25 45 100 2 25 24 76.5 3 40 12 99.9 4 40 6 99.9 5 40 4 99.3 6 40 2 98.9 7 c 40 12 37.6 a Reaction conditions: phenylacetylene (0.5 mmol), TfOH (20 mol %), H 2 O (2.0 equiv), TFE (1 ml), the yield was determined by GC with an internal standard (mesitylene). b The same reaction conditions as reference: Org. Lett. 2016, 18, 2184 2187. c Hexafluoro-2-propanol (HFIP) was used as solvent. 3. General Procedure for the Synthesis of Racemic Aryl Alcohols The aryl ketone (0.2 mmol) was dissolved in 1.0 ml MeOH, and NaBH 4 (0.4 mmol) was added slowly. The mixture was stirred at room temperature until the starting material was disappeared. And then 5.0 ml of H 2 O was added slowly, the residue was extracted 3 times with ethyl acetate. The combined organic layer was dried over Na 2 SO 4 and evaporated under reduced pressure. The product was further purified by silica gel column. 4. Reaction Conditions for Hydration and Asymmetric Hydrogenation Steps a 2

hydration step asymmetric hydrogenation step entry substrate product yield (%) ee (%) T/ o (S,S)-1c KOH H C t/h t/h 2 T/ o C (mol %) (equiv) (atm) 1 2a: R = H, R' = H 3a 40 6 0.5 0.25 24 20 40 96 99 2 2b: R = 2-F, R' = H 3b 70 12 0.5 0.25 24 20 40 90 93 3 2c: R = 3-F, R' = H 3c 70 12 0.5 0.25 24 20 40 81 99 4 2d: R = 4-F, R' = H 3d 70 12 0.5 0.25 24 20 40 96 95 5 2e: R = 4-Cl, R' = H 3e 70 12 0.5 0.25 24 20 40 94 91 6 2f: R = 2,5-Cl, R' = H 3f 70 12 0.5 0.25 24 20 40 79 87 7 2g: R = 3-Br, R' = H 3g 70 12 0.5 0.25 24 20 40 82 95 8 2h: R = 4-Br, R' = H 3h 70 12 0.5 0.25 24 20 40 89 97 9 b 2i: R = 4-NO 2, R' = H 3i 70 48 0.5 0.25 24 20 40 62 81 10 2j: R = 4-Me, R' = H 3j 40 6 0.5 0.25 24 20 40 85 99 11 2k: R = 4-Et, R' = H 3k 40 6 0.5 0.25 24 20 40 82 99 12 2l: R = 4-n-Pr, R' = H 3l 40 6 0.5 0.25 24 20 40 83 97 13 2m: R = 4-MeO, R' = H 3m 40 6 0.5 0.25 24 20 40 87 97 14 2n: 2-ethynylnaphthalene 3n 40 6 0.5 0.25 24 20 40 90 93 15 2o: R = H, R' = Me 3o 40 48 0.5 0.25 24 20 40 79 99 16 2p: R = H, R' = Et 3p 40 48 0.5 0.25 24 20 40 72 93 17 2q: R = H, R' = n-bu 3q 40 48 0.5 0.25 24 20 40 75 94 18 2r: R = H, R' = Ph 3r 40 48 0.5 0.25 24 20 40 83 97 a Reaction conditions: phenylacetylene (0.5 mmol), TfOH (20 mol %), H 2 O (2.0 equiv), TFE (1 ml), isolated yield. b Hexafluoro-2-propanol (HFIP) was used as solvent. 3

5. General Procedure for the Hydration and Asymmetric Hydrogenation of Alkynes Under nitrogen atmosphere, the alkyne (0.5 mmol), TfOH (0.1 mmol, 10 ul), H 2 O (1 mmol, 18.0 ul), and TFE (1.0 ml) were added into a 10 ml glass tube. The reaction mixture was stirred at 40 70 o C for 6 48 h. After the hydration reaction was complete, KOH (0.125 mmol, 7.0 mg) and (S,S)-1c (25 mmol, 1.59 mg) were added. The glass tube was put into a stainless steel autoclave. The final pressure of the hydrogen gas was adjusted to 20 atm after purging the autoclave with hydrogen gas 3 times. The reaction mixture was stirred at 40 o C for 24 h. The solvent was removed under reduced pressure. Water (2 ml) was added and extracted 3 times with ethyl acetate, and the combined organic layer was dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was further purified by silica gel column. 6. General Procedure for the Hydration and Asymmetric Hydrogenation of 1,3-diethynylbenzene Under nitrogen atmosphere, 1,3-diethynylbenzene (0.5 mmol), TfOH (0.2 mmol, 20 ul), H 2 O (2 mmol, 36 ul), and TFE (1.0 ml) were added into a 10 ml glass tube. The reaction mixture was stirred at 70 o C for 48 h. After the hydration reaction was complete, KOH (0.225 mmol, 12.6 mg) and (S,S)-1c (5 mmol, 3.18 mg) were added. The glass tube was put into a stainless steel autoclave. The final pressure of the hydrogen gas was adjusted to 40 atm after purging the autoclave with hydrogen gas 3 times. The reaction mixture was stirred at 40 o C for 24 h. The solvent was removed under reduced pressure. Water (2 ml) was added and extracted 3 times with ethyl acetate, and the combined organic layer was dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was further purified by silica gel column to give a colourless oil (74 mg, 89% yield, >99% ee, >99% de). 7. General Procedure for the Hydration and Asymmetric Hydrogenation of 1,4-diethynylbenzene 4

168.0 mg) and (S,S)-1c (0.6 mmol, 38.2 mg) were added. The glass tube was put into a stainless steel autoclave. The final pressure of the hydrogen gas was adjusted to 20 atm after purging the autoclave with hydrogen gas 3 times. The reaction mixture was stirred at 40 o C for 24 h. The solvent was removed under reduced pressure. Water (2 ml) was added and extracted 3 times with ethyl acetate, and the combined organic layer was dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was further purified by silica gel column to give a colourless oil (1.32 g, 92% yield, 99% ee). 10. Analytical Data of the Products (S)-1-phenylethanol (3a, CAS: 1445-91-6, know compound) [1] OH CH 3 Colourless oil; 96% yield (59 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -56.6 (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.43-7.37 (m, 4H), 7.34-7.30 (m, 1H), 4.93 (q, J = 6.4 Hz, 1H), 2.03 (s, 1H), 1.54 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 145.83, 128.53, 127.50, 125.41, 70.44, 25.19. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 97:3 (v/v), 1.0 ml/min, 254 nm, 30 ), t R = 11.58 min (minor), t S = 13.82 min (major). (S)-1-(2-fluorophenyl)ethanol (3b, CAS: 171032-87-4, know compound) [3] Colourless oil; 90% yield (63 mg), 93% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -43.4 (c 0.9, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.53-7.49 (m, 1H), 7.17-7.11 (m, 1H), 7.30-7.24 (m, 1H), 7.20-7.16 (m, 1H), 7.07-7.02 (m, 1H), 5.21 (q, J = 2.8 Hz, 1H), 2.47 (d, J = 3.2 Hz, 1H), 1.53 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 159.69 (d, J = 243.6 Hz, 1C), 132.68 (d, J = 13.2 Hz, 1C), 128.75 (d, J = 8.3 Hz, 1C), 126.64 (d, J = 4.5 Hz, 1C), 124.32 (d, J = 3.5 Hz, 1C), 115.27 (d, J = 21.8 Hz, 1C), 64.43 (d, J = 3.1 Hz, 1C), 24.01. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 254 nm, 30 = 11.56 min (major). ), t R = 10.71 min (minor), t S (S)-1-(3-fluorophenyl)ethanol (3c, CAS: 126534-32-5, know compound) [3] Colourless oil; 81% yield (58 mg), >99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -49.0 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.36-7.30 (m, 1H), 7.17-7.11 (m, 2H), 7.01-6.96 (m, 1H), 4.92 (q, J = 6.4 Hz, 1H), 2.14 (s, 1H), 1.51 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 163.00 (d, J = 244.2 Hz, 1C), 148.52 (d, J = 6.5 Hz, 1C), 129.99 (d, J = 8.0 Hz, 1C), 120.95 (d, J = 2.7 Hz, 1C), 114.21 (d, J = 21.0 Hz, 1C), 112.31 (d, J = 21.6 Hz, 1C), 69.80 (d, J = 1.8 Hz, 1C), 25.22. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 200 nm, 30 ), t S = 7.77 min (major). 6

(S)-1-(4-fluorophenyl)ethanol (3d, CAS: 101219-73-2, know compound) [3] Colourless oil; 96% yield (67 mg), 95% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -65.0 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.37-7.34 (m, 2H), 7.05 (t, J = 8.8 Hz, 2H), 4.90 (q, J = 6.8 Hz, 1H), 2.27 (s, 1H), 1.49 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 162.10 (d, J = 243.6 Hz, 1C), 141.53 (d, J = 3.2 Hz, 1C), 127.06 (d, J = 8.0 Hz, 2C), 115.24 (d, J = 21.2 Hz, 2C), 69.74, 25.27. HPLC (Chiralcel AS-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 220 nm, 30 ), t R = 13.86 min (minor), t S = 15.67 min (major). (S)-1-(4-chlorophenyl)ethanol (3e, CAS: 99528-42-4, know compound) [3] Colourless oil; 94% yield (73 mg), 91% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -59.3 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.37-7.32 (m, 4H), 4.90 (q, J = 6.4 Hz, 1H), 2.05 (s, 1H), 1.50 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 144.25, 133.07, 128.61, 126.81, 69.75, 25.29. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 97:3 (v/v), 1.0 ml/min, 220 nm, 30 ), t S = 10.76 min (major), t R = 11.92 min (minor). (S)-1-(2,5-dichlorophenyl)ethanol (3f, CAS: 691881-93-3, know compound) Colourless oil; 79% yield (74 mg), 87% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -72.5 (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.51 (d, J = 8.4 Hz, 1H), 7.43 (d, J = 2.0 Hz, 1H), 7.27 (dd, J 1 = 8.4 Hz, J 2 = 8.4 Hz, 1H), 5.21 (q, J = 6.4 Hz, 1H), 2.78 (s, 1H), 1.45 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 141.72, 133.34, 132.09, 129.06, 127.48, 127.41, 66.50, 23.58. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 220 nm, 30 ), t S = 18.96 min (major), t R = 21.04 min (minor). (S)-1-(3-bromophenyl)ethanol (3g, CAS: 134615-22-8, know compound) [2] Colourless oil; 82% yield (82 mg), 95% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -48.9 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.54 (t, J = 2.0 Hz, 1H), 7.43-7.40 (m, 1H), 7.30-7.28 (m, 1H), 7.23 (t, J = 7.6 Hz, 1H), 4.84 (q, J = 6.4 Hz, 1H), 2.56 (s, 1H), 1.48 (d, J = 6.8 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 148.14, 130.44, 130.11, 128.58, 124.05, 122.59, 69.69, 25.23. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 220 nm, 30 ), t S = 8.48 min (major), t R = 9.40 min (minor). (S)-1-(4-bromophenyl)ethanol (3h, CAS: 100760-04-1, know compound) [3] Colourless oil; 89% yield (88 mg), 97% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -31.9 (c 0.9, CHCl 3 )). 1 H NMR 7

(400 MHz, CDCl 3 ): δ = 7.50 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 4.90 (q, J = 6.4 Hz, 1H), 2.04 (s, 1H), 1.50 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 144.78, 131.56, 127.16, 121.17, 69.79, 25.26. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 ), t S = 8.37 min (major), t R = 9.10 min (minor). (S)-1-(4-nitrophenyl)ethanol (3i, CAS: 6531-13-1, know compound) [1] Colourless oil; 62% yield (52 mg), 81% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -22.2 (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 8.21 (d, J = 8.8 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 5.05 (q, J = 6.8 Hz, 1H), 2.37 (s, 1H), 1.54 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 153.17, 147.13, 126.15, 123.76, 69.50, 25.51. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 = 32.23 min (minor). ), t S = 30.10 min (major), t R (S)-1-(p-tolyl)ethanol (3j, CAS: 51154-54-2, know compound) [3] Colourless oil; 85% yield (57 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -60.1 (c 1.0, CHCl 3 ). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.31 (d, J = 7.6 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 4.91 (q, J = 6.4 Hz, 1H), 2.39 (s, 3H), 1.97 (s, 1H), 1.52 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 142.90, 137.16, 129.18, 125.38, 70.26, 25.10, 21.12. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 220 nm, 30 = 10.22 min (major), t R = 11.66 min (minor). ), t S (S)-1-(4-ethylphenyl)ethanol (3k, CAS: 101219-72-1, know compound) [2] Colourless oil; 82% yield (61.2 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -50.1 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.34 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 7.6 Hz, 2H), 4.92 (q, J = 6.8 Hz, 1H), 2.68 (q, J = 7.6 Hz, 2H), 1.79 (s, 1H), 1.53 (d, J = 6.4 Hz, 3H), 1.27 (t, J = 7.6 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 143.26, 143.09, 128.02, 125.45, 70.33, 28.55, 25.06, 15.66. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 254 nm, 30 min (major). ), t R = 19.09 min (minor), t S = 20.50 (S)-1-(4-propylphenyl)ethanol (3l, CAS: 473700-93-5, know compound) [2] OH Colourless oil; 83% yield (68 mg), 97% ee. Purified by flash column CH chromatography (PE: EA = 10:1). ([α] 20 D -49.1 (c 1.0, CHCl 3 )). 1 3 H H NMR (400 MHz, CDCl 3 ): δ = 7.33 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 3 C 8.0 Hz, 2H), 4.92 (q, J = 6.8 Hz, 1H), 2.62 (q, J = 7.2 Hz, 2H), 1.91 (s, 1H), 1.73-1.65 (m, 2H), 8

1.53 (d, J = 6.4 Hz, 3H), 0.99 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 143.08, 142.03, 128.59, 125.35, 70.31, 37.74, 25.03, 24.60, 13.87. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 97:3 (v/v), 1.0 ml/min, 254 nm, 30 min (major). ), t R = 8.16 min (minor), t S = 9.04 (S)-1-(4-methoxyphenyl)ethanol (3m, CAS: 1572-97-0, know compound) [1] Colourless oil; 87% yield (66 mg), 97% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -52.4 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.32 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 4.86 (q, J = 6.4 Hz, 1H), 3.83 (s, 3H), 2.22 (s, 1H), 1.50 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 158.92, 138.07, 126.70, 113.83, 69.93, 55.31, 25.05. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 220 nm, 30 11.62 min (minor), t S = 13.49 min (major). ), t R = (S)-1-(naphthalen-2-yl)ethanol (3n, CAS: 27544-18-9, know compound) [1] White solid, m. p. = 70-72, 90% yield (77 mg), 93% ee. Purified by flash column chromatography (PE: EA = 3:1). ([α] 20 D -42.5 (c, 0.70, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.89-7.85 (m, 4H), 7.56-7.49 (m, 3H), 5.11 (q, J = 7.2 Hz, 1H), 2.08 (s, 1H), 1.62 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 143.21, 133.34, 132.94, 128.34, 127.96, 127.70, 126.18, 125.83, 123.85, 123.83, 70.56, 25.17. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 230 nm, 30 ), t S = 24.01 min (major), t R = 32.61 min (minor). (S)-1-phenylpropan-1-ol (3o, CAS: 613-87-6, know compound) [3] Colourless oil; 79% yield (54 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -48.6 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.42-7.37 (m, 4H), 7.35-7.31 (m, 1H), 4.64 (t, J = 6.8 Hz, 1H), 1.91-1.78 (m, 3H), 0.96 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 144.59, 128.43, 127.54, 125.99, 76.07, 31.92, 10.19. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 min (minor). ), t S = 8.57 min (major), t R = 9.60 (S)-1-phenylbutan-1-ol (3p, CAS: 22135-49-5, know compound) [3] Yellow oil; 72% yield (54 mg), 93% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -48.1 (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.38 (d, J = 4.4 Hz, 4H), 7.33-7.30 (m, 1H), 4.74-4.70 (m, 1H), 1.90-1.81 (m, 2H), 1.79-1.64 (m, 1H), 1.49-1.45 (m, 1H), 1.38-1.29 (m, 1H), 0.97 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 144.93, 128.45, 127.52 125.92, 74.47, 9

41.27, 19.08, 14.01. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 254 nm, 30 ), t S = 14.10 min (major), t R = 15.61 min (minor). (S)-1-phenylhexan-1-ol (3q, CAS: 138381-77-8, know compound) [1] Colourless oil; 75% yield (67 mg), 94% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D -46.5 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.38 (dd, J 1 = 2.0 Hz, J 2 = 5.2 Hz, 4H), 7.33-7.31 (m, 1H), 4.68 (t, J = 6.4 Hz, 1H), 2.14 (s, 1H), 1.85-1.80 (m, 1H), 1.77-1.73 (m, 1H), 1.48-1.44 (m, 1H), 1.37-1.31 (m, 5H), 0.93 (t, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 145.00, 128.42, 127.46, 125.94, 74.70, 39.10, 31.77, 25.54, 22.61, 14.07. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 220 nm, 30 = 20.63 min (major). ), t R = 19.48 min (minor), t S (S)-1,2-diphenylethanol (3r, CAS: 5773-56-8, know compound) [4] White solid, m. p. = 60-61 ; 83% yield (82 mg), 97% ee. Purified by flash column chromatography (PE: EA = 5:1). ([α] 20 D -52.4 (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.41-7.24 (m, 10H), 4.97-4.93 (m, 1H), 3.12-3.00 (m, 2H), 1.99 (d, J = 2.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 143.81, 138.04, 129.53, 128.54, 128.45, 127.65, 126.66, 125.91, 75.38, 46.14. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 220 nm, 30 ), t R = 11.21 min (minor), t S = 12.25 min (major). (1S,1'S)-1,1'-(1,3-phenylene)diethanol (3s, CAS: 143329-81-1, know compound) [5],[6] Colourless oil; 89% yield (74 mg, de > 99%), >99% ee, Purified by flash column chromatography (PE: EA = 5:1). ([α] 20 D -61.5 (c, 1.0, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.38 (d, J = 6.0 Hz, 1H), 7.31 (d, J = 6.8 Hz, 1H), 7.24 (t, J = 6.8 Hz, 2H), 4.86 (q, J = 6.8 Hz, 2H), 2.78 (s, 2H), 1.48 (d, J = 6.4 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ): δ = 146.11, 146.08, 128.55, 128.53, 124.55, 124.51, 122.49, 122.37, 70.28, 70.25, 25.15, 25.10. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 ), t S,S = 17.70 min (major), t R,R = 20.84 min (minor). (1S,1'S)-1,1'-(1,4-phenylene)diethanol (3t, CAS: 143394-10-9, know compound) [5],[6] H 3 C OH OH CH 3 White solid, m. p. = 128-130 ; 92% yield (76 mg, de > 98%), 93% ee, Purified by flash column chromatography (PE: EA = 5:1). ([α] 20 D -87.5 (c 1.0, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.38 (s, 4H), 4.93 (q, J = 6.4 Hz, 2H), 2.03 (s, 2H), 1.52 (d, J = 6.4 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ): δ = 145.06, 125.58, 70.18, 70.16, 25.19. HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 90:10 (v/v), 1.0 ml/min, 210 nm, 30 ), t R,R = 12.28 min (minor), t S,S = 10

13.21 min (major), t meso = 17.22 min (minor). (1S,1'S,1''S)-1,1',1''-(benzene-1,3,5-triyl)triethanol (3u, unknow compound) Colourless oil; 91% yield (95 mg, de > 98%), 93% ee, Purified by flash column chromatography (PE: EA = 2:1). ([α] 20 D -46.2 (c, 1.0, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.43-7.41 (m, 3H), 4.90 (q, J = 6.4 Hz, 3H), 2.04 (s, 3H), 1.51 (d, J = 6.4 Hz, 9H); 13 C NMR (100 MHz, CDCl 3 ): δ = 146.39, 146.38, 128.23, 128.21, 123.07, 123.04, 122.30, 69.96, 69.94, 25.21, 25.19. HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 80:20 (v/v), 1.0 ml/min, 254 nm, 30 ), t R,R,R = 4.21 min (minor), t S,S,S = 5.28 min (major). HRMS (ESI) m/z [M-H] - calcd for C 12 H 18 O 3 209.1183, found: 209.1182. Reference: [1] Zhang, Z.; Jain, P.; Antilla, J. C. Angew. Chem., Int. Ed. 2011, 50, 10961 10964. [2] Li, F.; Wang, N.; Lu, L.; Zhu, G. J. J. Org. Chem. 2015, 80, 3538 3546. [3] Chen, X.; Lu, Z. Org. Lett. 2016, 18, 4658 4661. [4] Li, J.; Wang, C.; Xue, D.; Wei, Y.; Xiao, J. Green Chem. 2013, 15, 2685-2689. [5] Shimada, Y.; Miyake, Y.; Matsuzawa, H.; Nishibayashi Y., Chem. Asian J. 2007, 2, 393 396. [6] Uchiyama, M.; Katoh, N.; Mimura, R., Yokota, N., Shimogaichi, Y., Shimazaki, M., Ohta, A. Tetrahedron: Asymmetry, 1997, 8, 3467-3474. 11

11. 1 H NMR and 13 C NMR Spectra of the Products 12

13

14

15

16

17

18

19

20

OH CH 3 H 3 C 3j 21

22

23

24

25

26

OH CH 3 3p 27

28

29

30

31

CH 3 OH HO CH 3 H 3 C OH CH 3 OH HO CH 3 H 3 C OH 32

12. HPLC Spectra of the Products OH CH 3 3a 0.12 0.10 0.08 11.465 13.865 0.06 0.04 0.02 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 1 11.465 2118457 50.01 117993 bb 2 13.865 2117822 49.99 101248 bb OH CH 3 0.20 13.824 0.15 0.10 0.05 11.589 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 1 11.588 23308 0.42 2250 bb 2 13.824 4440217 99.58 200605 bb 33

3b 0.070 0.060 10.635 11.407 0.050 0.040 0.030 0.020 0.010 0 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 1 10.635 1175759 49.76 68837 bb 2 11.407 1187210 50.24 65875 bb 0.70 0.60 11.565 0.50 0.40 0.30 0.20 0.10 10.719 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 1 10.719 521729 3.47 31266 bb 2 11.565 12635160 96.53 679429 bb 34

3c 1.50 5.892 7.230 1.00 0.50 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 1 5.892 28128690 50.12 1639654 bb 2 7.230 27990295 49.88 1105522 bb 0.20 7.779 0.10 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 1 7.779 6055541 10 272838 bb 35

3d 0.10 0.08 13.783 15.625 0.06 0.04 0.02-0.02 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 1 13.783 4940957 49.31 121737 bb 2 15.625 5078763 50.69 113990 bb 0.08 15.672 0.06 0.04 0.02 13.860 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 1 13.860 93519 2.47 2942 bb 2 15.672 3686501 97.53 92422 bb 36

3e 1.20 1.00 10.743 11.918 0.80 0.60 0.40 0.20 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 15.00 16.00 1 10.743 19567901 50.04 1241972 bb 2 11.918 19536517 49.96 1172397 bb 0.70 0.60 10.746 0.50 0.40 0.30 0.20 0.10 11.920 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 15.00 16.00 1 10.746 11499407 95.91 753199 bb 2 11.920 489961 4.09 39325 bb 37

3f 0.50 0.40 17.859 26 0.30 0.20 0.10 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 1 17.859 19026005 50.16 497090 bb 2 26 18904174 49.84 471250 bb 2.20 2.00 1.80 18.962 1.60 1.40 1.20 1.00 0.80 0.60 0.40 0.20 21.041 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 1 18.962 78278689 93.51 2213443 bb 2 21.041 5429347 6.49 158324 bb 38

3g 1.40 1.20 8.402 9.217 1.00 0.80 0.60 0.40 0.20 2.00 4.00 6.00 8.00 1 12.00 14.00 1 8.402 17421213 49.76 1487118 bb 2 9.217 17586816 50.24 1337508 bb 3.00 8.487 2.50 2.00 1.50 1.00 0.50 9.401 2.00 4.00 6.00 8.00 1 12.00 14.00 1 8.487 54928552 97.93 3181975 bb 2 9.401 1162568 2.07 106985 bb 39

3h 0.35 0.30 0.25 8.451 9.119 0.20 0.15 0.10 0.05 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 1 8.451 4185450 49.83 335018 bb 2 9.119 4214619 50.17 296990 bb 0.10 8.377 0.08 0.06 0.04 0.02 9.103 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 1 8.377 1316613 98.97 110411 bb 2 9.103 13768 1.03 1651 bb 40

OH CH 3 O 2 N 3i 0.20 0.15 28.443 30.452 0.10 0.05 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 32.00 34.00 36.00 1 28.443 11601540 50.71 222898 bb 2 30.452 11276947 49.29 194518 bb OH O 2 N CH 3 0.10 0.08 30.104 0.06 0.04 0.02 32.267 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 32.00 34.00 36.00 38.00 1 30.104 5762802 90.97 99893 Bb 2 32.237 572026 9.03 12445 bb 41

3j 1.40 1.20 1.00 10.143 11.594 0.80 0.60 0.40 0.20 2.00 4.00 6.00 8.00 1 12.00 14.00 1 10.143 35426399 49.58 1410791 bb 2 11.594 36025226 50.42 1226451 bb 1.40 1.20 10.222 1.00 0.80 0.60 0.40 0.20 11.667 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 1 10.222 46288860 99.81 1457608 bb 2 11.667 87142 0.19 5371 bb 42

3k 0.030 19.212 20.814 0.020 0.010 0 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 1 19.212 1014161 50.09 35004 bb 2 20.814 1010695 49.91 28295 bb 0.050 0.040 20.501 0.030 0.020 0.010 19.099 0 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 1 19.099 5710 0.35 314 bb 2 20.501 1621065 99.65 47502 bb 43

3l 0.060 0.050 8.264 9.151 0.040 0.030 0.020 0.010 0 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 1 8.264 760080 50.44 57999 bb 2 9.151 746896 49.56 50788 bb 0.08 9.048 0.06 0.04 0.02 8.166 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 1 8.166 14260 1.05 1383 bb 2 9.048 1343951 98.95 91118 bb 44

3m 0.12 0.10 0.08 11.465 13.865 0.06 0.04 0.02 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 1 11.465 2118457 50.01 117993 bb 2 13.665 2117822 49.99 101248 bb 1.20 13.492 1.00 0.80 0.60 0.40 0.20 11.621 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 1 11.621 269225 1.03 22017 bb 2 13.492 25848382 98.97 1293140 bb 45

3n 0.50 0.40 24.098 32.288 0.30 0.20 0.10 5.00 1 15.00 2 25.00 3 35.00 4 45.00 1 24.098 36925337 48.20 485298 bb 2 32.288 39684986 51.80 390175 bb 0.70 0.60 24.013 0.50 0.40 0.30 0.20 0.10 32.619 5.00 1 15.00 2 25.00 3 35.00 4 45.00 1 24.013 59044636 96.94 721648 bb 2 32.619 1865168 3.06 28695 bb 46

3o 0.30 0.25 0.20 8.151 9.200 0.15 0.10 0.05 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 1 8.151 4088101 51.68 294285 bb 2 9.200 3823016 48.32 265718 bb 0.050 8.578 0.040 0.030 0.020 0.010 9.608 0 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 1 8.578 682370 99.81 55572 bb 2 9.608 1300 0.19 136 bb 47

3p 0.12 0.10 14.213 15.260 0.08 0.06 0.04 0.02 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 1 14.213 2689042 50.61 115927 bb 2 15.260 2623979 49.39 102692 bb 0.014 0.012 14.101 0.010 8 6 4 2 15.619 0 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 1 14.101 272991 96.76 13153 bb 2 15.619 9153 3.24 505 bb 48

3q 0.16 0.14 19.032 20.733 0.12 0.10 0.08 0.06 0.04 0.02 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 1 19.032 4795474 50.02 159947 bb 2 20.733 4791335 49.98 138208 bb 0.22 0.20 0.18 20.632 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 19.484 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 1 19.484 247287 2.87 9460 bb 2 20.632 8360926 97.13 212523 bb 49

3r 0.60 0.50 0.40 10.821 12.739 0.30 0.20 0.10 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 1 10.821 10518942 49.12 594959 bb 2 12.739 10894739 50.88 388223 bb 2.50 2.00 12.254 1.50 1.00 11.215 0.50 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 1 11.215 752008 1.39 60150 bb 2 12.254 53465877 98.61 2593306 bb 50

3s 0.035 0.030 0.025 17.897 20.841 0.020 0.015 0.010 5 29.928 32.239 0 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 32.00 34.00 36.00 38.00 4 1 17.897 1598497 42.08 36650 bb 2 20.841 1586914 41.77 32729 bb 3 29.928 321781 8.47 5918 bb 4 32.239 291888 7.68 4754 bb 0.30 0.25 17.700 0.20 0.15 0.10 0.05 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 22.00 24.00 26.00 28.00 3 32.00 34.00 36.00 38.00 4 1 17.700 14233192 10 317550 bb 51

3t 1.60 1.40 1.20 12.238 13.217 17.054 1.00 0.80 0.60 0.40 0.20 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 1 12.238 26513708 24.93 1234636 BV 2 13.217 26868476 25.27 1143585 VB 3 17.054 52963234 49.80 1692842 BB 2.40 2.20 2.00 13.168 1.80 1.60 1.40 1.20 1.00 0.80 0.60 0.40 0.20 17.333 2.00 4.00 6.00 8.00 1 12.00 14.00 16.00 18.00 2 1 13.168 58124914 95.00 2350971 bb 2 17.333 3057095 5.00 111879 bb 52

3u 0.24 0.22 0.20 7.840 0.18 0.16 6.704 0.14 0.12 8.959 0.10 0.08 0.06 0.04 4.899 5.394 5.927 0.02 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 1 4.899 1079083 7.54 46623 VV 2 5.394 1054358 7.37 62542 VV 3 5.927 547068 3.82 29502 VV 4 6.704 3248523 22.69 153727 VV 5 7.840 5429110 37.93 229104 VV 6 8.959 2956539 20.65 113905 VB 0.10 5.286 0.08 0.06 0.04 0.02 4.215 7.516 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 1 11.00 12.00 13.00 14.00 1 4.215 47155 2.48 4366 bb 2 5.286 1843832 96.98 111223 bb 3 7.516 10268 0.54 952 bb 53