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

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1 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 , China Yichang Humanwell Pharmaceutical Co., Ltd, Yichang, , 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 S H NMR and 13 C NMR Spectra of the Products...S HPLC Spectra of Products....S33 1

2 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 ( 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 c 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, 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

3 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 b: R = 2-F, R' = H 3b c: R = 3-F, R' = H 3c d: R = 4-F, R' = H 3d e: R = 4-Cl, R' = H 3e f: R = 2,5-Cl, R' = H 3f g: R = 3-Br, R' = H 3g h: R = 4-Br, R' = H 3h b 2i: R = 4-NO 2, R' = H 3i j: R = 4-Me, R' = H 3j k: R = 4-Et, R' = H 3k l: R = 4-n-Pr, R' = H 3l m: R = 4-MeO, R' = H 3m n: 2-ethynylnaphthalene 3n o: R = H, R' = Me 3o p: R = H, R' = Et 3p q: R = H, R' = n-bu 3q r: R = H, R' = Ph 3r 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

4 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 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

6 168.0 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: , 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 (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 4H), (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 = , , , , 70.44, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 97:3 (v/v), 1.0 ml/min, 254 nm, 30 ), t R = min (minor), t S = min (major). (S)-1-(2-fluorophenyl)ethanol (3b, CAS: , know compound) [3] Colourless oil; 90% yield (63 mg), 93% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 0.9, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 1H), (m, 1H), (m, 1H), (m, 1H), (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 = (d, J = Hz, 1C), (d, J = 13.2 Hz, 1C), (d, J = 8.3 Hz, 1C), (d, J = 4.5 Hz, 1C), (d, J = 3.5 Hz, 1C), (d, J = 21.8 Hz, 1C), (d, J = 3.1 Hz, 1C), HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 254 nm, 30 = min (major). ), t R = min (minor), t S (S)-1-(3-fluorophenyl)ethanol (3c, CAS: , know compound) [3] Colourless oil; 81% yield (58 mg), >99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 1H), (m, 2H), (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 = (d, J = Hz, 1C), (d, J = 6.5 Hz, 1C), (d, J = 8.0 Hz, 1C), (d, J = 2.7 Hz, 1C), (d, J = 21.0 Hz, 1C), (d, J = 21.6 Hz, 1C), (d, J = 1.8 Hz, 1C), 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

7 (S)-1-(4-fluorophenyl)ethanol (3d, CAS: , know compound) [3] Colourless oil; 96% yield (67 mg), 95% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (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 = (d, J = Hz, 1C), (d, J = 3.2 Hz, 1C), (d, J = 8.0 Hz, 2C), (d, J = 21.2 Hz, 2C), 69.74, HPLC (Chiralcel AS-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 220 nm, 30 ), t R = min (minor), t S = min (major). (S)-1-(4-chlorophenyl)ethanol (3e, CAS: , know compound) [3] Colourless oil; 94% yield (73 mg), 91% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (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 = , , , , 69.75, HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 97:3 (v/v), 1.0 ml/min, 220 nm, 30 ), t S = min (major), t R = min (minor). (S)-1-(2,5-dichlorophenyl)ethanol (3f, CAS: , know compound) Colourless oil; 79% yield (74 mg), 87% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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 = , , , , , , 66.50, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 220 nm, 30 ), t S = min (major), t R = min (minor). (S)-1-(3-bromophenyl)ethanol (3g, CAS: , know compound) [2] Colourless oil; 82% yield (82 mg), 95% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.54 (t, J = 2.0 Hz, 1H), (m, 1H), (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 = , , , , , , 69.69, 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: , know compound) [3] Colourless oil; 89% yield (88 mg), 97% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 0.9, CHCl 3 )). 1 H NMR 7

8 (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 = , , , , 69.79, 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: , know compound) [1] Colourless oil; 62% yield (52 mg), 81% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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 = , , , , 69.50, HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 = min (minor). ), t S = min (major), t R (S)-1-(p-tolyl)ethanol (3j, CAS: , know compound) [3] Colourless oil; 85% yield (57 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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 = , , , , 70.26, 25.10, HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 220 nm, 30 = min (major), t R = min (minor). ), t S (S)-1-(4-ethylphenyl)ethanol (3k, CAS: , know compound) [2] Colourless oil; 82% yield (61.2 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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 = , , , , 70.33, 28.55, 25.06, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 254 nm, 30 min (major). ), t R = min (minor), t S = (S)-1-(4-propylphenyl)ethanol (3l, CAS: , 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 (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), (m, 2H), 8

9 1.53 (d, J = 6.4 Hz, 3H), 0.99 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , 70.31, 37.74, 25.03, 24.60, 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: , know compound) [1] Colourless oil; 87% yield (66 mg), 97% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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 = , , , , 69.93, 55.31, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 220 nm, min (minor), t S = min (major). ), t R = (S)-1-(naphthalen-2-yl)ethanol (3n, CAS: , 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 (c, 0.70, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 4H), (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 = , , , , , , , , , , 70.56, HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 230 nm, 30 ), t S = min (major), t R = min (minor). (S)-1-phenylpropan-1-ol (3o, CAS: , know compound) [3] Colourless oil; 79% yield (54 mg), 99% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 4H), (m, 1H), 4.64 (t, J = 6.8 Hz, 1H), (m, 3H), 0.96 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , 76.07, 31.92, 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: , know compound) [3] Yellow oil; 72% yield (54 mg), 93% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (c 0.8, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.38 (d, J = 4.4 Hz, 4H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), 0.97 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = , , , 74.47, 9

10 41.27, 19.08, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 98:2 (v/v), 1.0 ml/min, 254 nm, 30 ), t S = min (major), t R = min (minor). (S)-1-phenylhexan-1-ol (3q, CAS: , know compound) [1] Colourless oil; 75% yield (67 mg), 94% ee. Purified by flash column chromatography (PE: EA = 10:1). ([α] 20 D (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), (m, 1H), 4.68 (t, J = 6.4 Hz, 1H), 2.14 (s, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 5H), 0.93 (t, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , 74.70, 39.10, 31.77, 25.54, 22.61, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 99:1 (v/v), 1.0 ml/min, 220 nm, 30 = min (major). ), t R = min (minor), t S (S)-1,2-diphenylethanol (3r, CAS: , know compound) [4] White solid, m. p. = ; 83% yield (82 mg), 97% ee. Purified by flash column chromatography (PE: EA = 5:1). ([α] 20 D (c 1.0, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 10H), (m, 1H), (m, 2H), 1.99 (d, J = 2.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , 75.38, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 220 nm, 30 ), t R = min (minor), t S = min (major). (1S,1'S)-1,1'-(1,3-phenylene)diethanol (3s, CAS: , 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 (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 = , , , , , , , , 70.28, 70.25, 25.15, HPLC (Chiralcel OJ-H column, n-hexane/2-propanol = 95:5 (v/v), 1.0 ml/min, 254 nm, 30 ), t S,S = min (major), t R,R = min (minor). (1S,1'S)-1,1'-(1,4-phenylene)diethanol (3t, CAS: , know compound) [5],[6] H 3 C OH OH CH 3 White solid, m. p. = ; 92% yield (76 mg, de > 98%), 93% ee, Purified by flash column chromatography (PE: EA = 5:1). ([α] 20 D (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 = , , 70.18, 70.16, HPLC (Chiralcel OD-H column, n-hexane/2-propanol = 90:10 (v/v), 1.0 ml/min, 210 nm, 30 ), t R,R = min (minor), t S,S = 10

11 13.21 min (major), t meso = 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 (c, 1.0, acetone)). 1 H NMR (400 MHz, CDCl 3 ): δ = (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 = , , , , , , , 69.96, 69.94, 25.21, 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 , found: Reference: [1] Zhang, Z.; Jain, P.; Antilla, J. C. Angew. Chem., Int. Ed. 2011, 50, [2] Li, F.; Wang, N.; Lu, L.; Zhu, G. J. J. Org. Chem. 2015, 80, [3] Chen, X.; Lu, Z. Org. Lett. 2016, 18, [4] Li, J.; Wang, C.; Xue, D.; Wei, Y.; Xiao, J. Green Chem. 2013, 15, [5] Shimada, Y.; Miyake, Y.; Matsuzawa, H.; Nishibayashi Y., Chem. Asian J. 2007, 2, [6] Uchiyama, M.; Katoh, N.; Mimura, R., Yokota, N., Shimogaichi, Y., Shimazaki, M., Ohta, A. Tetrahedron: Asymmetry, 1997, 8,

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

13 13

14 14

15 15

16 16

17 17

18 18

19 19

20 20

21 OH CH 3 H 3 C 3j 21

22 22

23 23

24 24

25 25

26 26

27 OH CH 3 3p 27

28 28

29 29

30 30

31 31

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

33 12. HPLC Spectra of the Products OH CH 3 3a bb bb OH CH bb bb 33

34 3b bb bb bb bb 34

35 3c bb bb bb 35

36 3d bb bb bb bb 36

37 3e bb bb bb bb 37

38 3f bb bb bb bb 38

39 3g bb bb bb bb 39

40 3h bb bb bb bb 40

41 OH CH 3 O 2 N 3i bb bb OH O 2 N CH Bb bb 41

42 3j bb bb bb bb 42

43 3k bb bb bb bb 43

44 3l bb bb bb bb 44

45 3m bb bb bb bb 45

46 3n bb bb bb bb 46

47 3o bb bb bb bb 47

48 3p bb bb bb bb 48

49 3q bb bb bb bb 49

50 3r bb bb bb bb 50

51 3s bb bb bb bb bb 51

52 3t BV VB BB bb bb 52

53 3u VV VV VV VV VV VB bb bb bb 53

Table of Contents 1. General General procedure and product characterization data for Table ,3-Dione substrates characterization da

Table of Contents 1. General General procedure and product characterization data for Table ,3-Dione substrates characterization da Supporting Information Wiley-VCH 2013 69451 Weinheim, Germany Highly Enantioselective Construction of 3-Hydroxy xindoles through a Decarboxylative Aldol Addition of Trifluoromethyl a-fluorinated gem-diols