## 3 Materials and Methods  
### General  
All chemical reagents and solvents were obtained from commercial suppliers. Chloromethylated polystyrene resin, cross-linked with 1% DVB (200-400 mesh, 1.3 mmol/g of Cl), was obtained from Tokyo Chemical Industry Co., Ltd. (Tokyo, Japan). Omnipore membrane filters (0.2 \(\upmu\)m pore size, 80% porosity) were supplied by Merck Co., Inc. (Darmstadt, Germany). Column chromatography was performed using silica gel 60 purchased from Kanto Chemical Co., Inc. (Tokyo, Japan). \({}^{1}\)H-NMR spectra were recorded on a JEOL ECA400 spectrometer (400 MHz for \({}^{1}\)H-NMR and 100 MHz for \({}^{13}\)C-NMR). Chemical shifts in \({}^{1}\)H-NMR were reported downfield from TMS (\(\delta\) = 0 ppm). For \({}^{13}\)C-NMR, chemical shifts were referenced to the solvent used as an internal standard. FT-IR spectra were recorded on a Shimadzu IRAffinity spectrometer. Elemental analyses were performed at Osaka University. Scanning probe microscopy (SPM) observations were performed at Shimadzu Corporation (Kyoto, Japan). Hydroxyamide-functionalized benzimidazole **1** was synthesized following our previously published procedure [47]. 1-[2-((S)-1-hydroxy-4-methyl-2-pentanylamino)-2-oxoethyl]-3-benzylbenzamideimidazole (**1**): \({}^{1}\)H-NMR (DMSO-\(d\delta\)) \(\delta\) = 8.16-8.11 (m, 2H), 7.66 (d, \(J\) = 8.2 Hz, 1H), 7.43-7.41 (d, 1H), 7.25-7.17 (m, 2H), 4.93 (d, \(J\) = 16.0 Hz, 1H), 4.87 (d, \(J\) = 16.0 Hz, 1H), 4.74 (t, \(J\) = 6.4 Hz, 1H), 3.84-3.75 (m, 1H), 3.35-3.26 (m, 2H), 1.64-1.54 (m, 2H), 1.33-1.30 (m, 1H), 0.86 (d, \(J\) = 6.4 Hz, 3H), 0.79 (d, \(J\) = 6.4 Hz, 3H); 13C-NMR (DMSO-\(d\delta\)) \(\delta\)=166.0, 144.9, 143.2, 134.2, 122.2, 121.5, 119.3, 110.1, 63.6, 49.1, 46.9, 24.2, 23.3, 21.8. NMR charts can be found in the Supplementary Materials. \begin{table}
\begin{tabular}{c c c c c c c} \hline \hline
**Entry** & **Substrate** & & **Catalytic System** & **Product** & **Yield [\%] 1** & **Ee [\%] 2** \\ \hline
1 & **7** & run 1 [3,4] & [IrCl(cod)]\({}_{2}\) combined with PS-**L3** [FOOTNOTE:1]Footnote 1: Isolated yield. 2 Determined by LC on a chiral stationary phase. 3 The catalytic reaction was performed as follows: A mixture of [IrCl(cod)]\({}_{2}\) (0.015 mmol, 10 mg), PS-**L3** (0.03 mmol, 42 mg), and Ag-CO\({}_{3}\) (0.015 mmol, 4 mg) within THF (2 mL) was stirred for 3 h, followed by the addition of (EtO)-MeSiII (2.25 mmol, 302 mg). After stirring for 20 h, ketone (0.5 mmol), K\({}_{2}\)CO\({}_{3}\) (5 mg), and MeOH (2 mL) were added. The resulting mixture was then allowed to react for 6 h. 4 The same data are presented in Table 3, entry 2. 5 The solid-state resin **X** (or **Y**) was recovered as follows: After the catalytic reaction, the resulting mixture was filtered through a membrane filter (pore size: 0.2 \(\upmu\)m). The recovered resin **X** (or **Y**) was then washed thoroughly with MeOH. 6 The catalytic reaction was performed with **X** (45 mg) instead of PS-**L3**. 7 The catalytic reaction was performed with **X** (45 mg) instead of PS-**L3**, without [IrCl(cod)]\({}_{2}\). 8 The same data are presented in Table 3, entry 7. 9 The catalytic reaction was performed with **Y** (49 mg) instead of PS-**L3**. 8 The same data are presented in Table 3, entry 7. 9 The catalytic reaction was performed with **Y** (49 mg) instead of PS-**L3**. 8 The same data are presented in Table 3, entry 2. 5 The solid-state resin **X** (or **Y**) was recovered as follows: After the catalytic reaction, the resulting mixture was filtered through a membrane filter (pore size: 0.2 \(\upmu\)m). The recovered resin **X** (or **Y**) was then washed thoroughly with MeOH. 6 The catalytic reaction was performed with **X** (45 mg) instead of PS-**L3**. 7 The catalytic reaction was performed with **X** (45 mg) instead of PS-**L3**, without [IrCl(cod)]\({}_{2}\). 8 The same data are presented in Table 3, entry 7. 9 The catalytic reaction was performed with **Y** (49 mg) instead of PS-**L3**. 9 The catalytic reaction was performed with **Y** (49 mg) instead of PS-**L3**.