## 3 Materials and Methods
### General Procedure for Catalytic Asymmetric Reduction of Ketone with (EtO)\({}_{2}\)MeSiH  
A mixture of [IrCl(cod)]\({}_{2}\) (0.015 mmol, 10 mg), PS-**L**3 (0.03 mmol, 42 mg), and Ag\({}_{2}\)CO\({}_{3}\) (0.015 mmol, 4 mg) was stirred in THF (2 mL) at room temperature for 3 h. (EtO)\({}_{2}\)MeSiH (2.25 mmol, 302 mg) was then added, and the mixture was stirred at room temperature for an additional 20 h. Following this, ketone (0.50 mmol), K\({}_{2}\)CO\({}_{3}\) (5 mg), and MeOH (2 mL) were added, and the mixture was stirred at room temperature for 6 h. Finally, the reaction mixture was filtered through a membrane filter (pore size: 0.2 \(\upmu\)m). The solid-state resin was then washed repeatedly with MeOH, yielding 45 mg of recovered resin. Meanwhile, the filtrate was concentrated under reduced pressure using a rotary evaporator. The resulting residue was purified by column chromatography on silica gel using a hexanes/EtOAc (9/1) solvent system to obtain the corresponding alcohol product. Enantiomeric excess (ee) values were determined by chiral GC or chiral LC, following our previously reported procedure [45]. The results of the GC or LC analysis are provided in the Supplementary Materials.  
1-Phenylethanol (**4**): \({}^{1}\)H-NMR (CDCl\({}_{3}\)) \(\delta\) = 7.40-7.25 (m, 5H), 4.90 (q, J = 6.4 Hz, 1H), 3.53 (br, 1H), 1.50 (d, J = 6.4 Hz, 3H); \({}^{13}\)C-NMR (CDCl\({}_{3}\)) \(\delta\) = 145.8, 128.5, 127.4, 125.4, 70.4, 25.1.  
1-Phenyl-1-propanol (**6**): \({}^{1}\)H-NMR (CDCl\({}_{3}\)) \(\delta\) = 7.35-7.26 (m, 5H), 4.59 (t, J = 6.4 Hz, 1H), 3.53 (br, 1H), 1.84-1.71 (m, 2H), 0.92 (t, J = 6.4 Hz, 3H); \({}^{13}\)C-NMR (CDCl\({}_{3}\)) \(\delta\) = 144.6, 128.4, 127.5, 125.9, 76.0, 31.9, 10.1.  
1-Phenyl-1-butanol (8): \({}^{1}\)H-NMR (CDCl\({}_{3}\)) \(\delta\) = 7.18-7.10 (m, 5H), 4.48 (t, J = 6.4 Hz, 1H), 1.64-1.58 (m, 1H), 1.55-1.46 (m, 1H), 1.32-1.21 (m, 1H), 1.19-1.08 (m, 2H), 0.77 (t, J = 7.2 Hz, 3H); \({}^{13}\)C-NMR (CDCl\({}_{3}\)) \(\delta\) = 144.9, 128.3, 127.3, 125.8, 74.3, 41.2, 18.9, 13.9.  
1-Phenyl-1-pentanol (10): \({}^{1}\)H-NMR (CDCl\({}_{3}\)) \(\delta\) = 7.33-7.24 (m, 5H), 4.64-4.60 (m, 1H), 1.83-1.64 (m, 3H), 1.43-1.34 (m, 2H), 1.28-1.19 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H); \({}^{13}\)C-NMR (CDC\({}_{3}\)) \(\delta\) = 144.9, 128.4, 127.4, 125.9, 74.6, 38.8, 27.9, 22.6, 14.0.  
Cyclohexyl(phenyl)methanol (**12**): \({}^{1}\)H-NMR (CDC\({}_{3}\)) \(\delta\) = 7.35-7.26 (m, 5H), 4.36 (dd, J = 7.2 and 3.2 Hz, 1H), 1.98 (d, J = 12.8 Hz, 1H), 1.83-1.75 (m, 2H), 1.65-1.57 (m, 4H), 1.40-1.35 (m, 1H), 1.24-0.91 (m, 4H); \({}^{13}\)C-NMR (CDC\({}_{3}\)) \(\delta\) = 143.6, 128.2, 127.4, 126.6, 79.4, 44.9, 29.3, 28.8, 26.4, 26.1, 26.0.  
1-(4-Butylphenyl)ethanol (**14**): \({}^{1}\)H-NMR (CDC\({}_{3}\)) \(\delta\) = 7.27 (d, J = 7.6 Hz, 2H), 7.16 (d, J = 7.6 Hz, 2H), 4.86 (q, J = 6.4 Hz, 1H), 2.60 (t, J = 7.6 Hz, 2H), 1.91 (br, 1H), 1.63-1.55 (m, 2H), 1.48 (d, J = 6.4 Hz, 3H), 1.40-1.31 (m, 2H), 0.92 (t, J = 7.6 Hz, 3H); \({}^{13}\)C-NMR (CDC\({}_{3}\)) \(\delta\) = 143.0, 142.2, 128.5, 125.3, 70.2, 35.2, 33.6, 25.0, 22.3, 13.9.  
1-(4-Methoxyphenyl)ethanol (**16**): \({}^{1}\)H-NMR (CDC\({}_{3}\)) \(\delta\) = 7.31-7.26 (m, 2H), 6.89-6.86 (m, 2H), 4.84 (q, J = 6.4 Hz, 1H), 3.80 (s, 3H), 1.94 (br, 1H), 1.47 (d, J = 6.8 Hz, 3H); \({}^{13}\)C-NMR (CDC\({}_{3}\)) \(\delta\) = 158.9, 138.0, 126.6, 113.8, 69.9, 55.2, 25.0.  
1-(4-Chlorophenyl)propanol (**18**): 1H-NMR (CDCl3) \(\delta\) = 7.32-7.25 (m, 4H), 4.57 (t, \(J\) = 6.4 Hz, 3H), 1.94 (br, 1H), 1.82-1.67 (m, 2H), 0.90 (t, \(J\) = 7.2 Hz, 3H); 13C-NMR (CDCl3) \(\delta\) = 142.9, 133.0, 128.5, 127.3, 75.2, 31.9, 9.9.  
1-(2-Naphthyt)ethanol (**20**): 1H-NMR (CDCl3) \(\delta\) = 7.80-7.74 (m, 4H), 7.46-7.41 (m, 3H), 4.98 (q, \(J\) = 6.4 Hz, 1H), 1.87 (br, 1H), 1.53 (d, \(J\) = 6.4 Hz, 3H); 13C-NMR (CDCl3) \(\delta\) = 143.2, 133.3, 132.8, 128.2, 127.9, 127.6, 126.1, 125.7, 123.8, 123.7, 70.4, 25.0.