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1 Supporting Information Wiley-VCH Weinheim, Germany Catalytic Hydrogenation of Cyclic Carbonates: A Practical Approach from C 2 and Epoxides to Methanol and Diols** Zhaobin Han, Liangce Rong, Jiang Wu, Lei Zhang, Zheng Wang, and Kuiling Ding* anie_ _sm_miscellaneous_information.pdf

2 Table of Contents 1. General Experimental... S2 2. General procedure for the synthesis of Ru complexes 1a-1e and 3... S2 3. General procedure for the preparation of cyclic carbonates... S4 4. General procedure for the hydrogenation of cyclic carbonates... S6 5. Complementary reaction optimization data... S8 6. Hydrogenative depolymerization of poly(propylene carbonate) (PPC) to methanol and propylene glycol... S10 7. Deuteration of ethylene carbonate and tetramethylethylene carbonate... S11 8. Catalytic hydrogenation of (R)-propylene carbonate... S12 9. Catalytic racemization of (R)-1,2-propanediol... S Control Experiments... S GC charts of the hydrogenation reaction products... S NMR spectra of the catalysts and products... S24 References... S33

3 1. General Experimental All reactions and manipulations were performed using standard Schlenk techniques. THF, 1,4- dioxane, and toluene were distilled from sodium benzophenone ketyl. 1 H, 13 C and 31 P NMR spectra were recorded on Varian Mercury 300 MHz or 400 MHz spectrometers. Chemical shifts (δ values) were reported in ppm relative to internal TMS ( 1 H NMR) or CDCl 3 ( 13 C NMR) and external 85% H 3 P 4 ( 31 P NMR), respectively. The following abbreviations (or combinations thereof) were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, b = broad. The IR spectra were measured on a Bio-Rad FTS-185 FT-IR spectrometer. EI (70 ev) and MALDI-TF mass spectra were obtained on Agilent 5973N and MATRIX VYAGR-DE STR spectrometers, respectively. HRMS(MALDI) was determined on IonSpect 4.7 TESLA FTMS spectrometers. GC analyses were carried out on an Agilent 6890 gas chromatograph using a DM-Wax column (60 m 0.32 mm 1 μm), Supelco GAMMA- DEX TM 225 column (30 m 0.25 mm 0.25 μm) or Supelco BATA-DEXTM 120 column (30 m 0.25 mm 0.25 μm). RuHCl(C)(PPh 3 ) [1] 3, HCl HN(CH 2 CH 2 PPh 2 ) [2] 2 and (Ph 2 PCH 2 CH 2 ) 2 NMe [3] were prepared according to the literature procedures. Ligands HN(CH 2 CH 2 P i Pr 2 ) 2, NH(tBu 2 PCH 2 CH 2 ) 2, HN(CH 2 CH 2 PCy 2 ) 2, HN(CH 2 CH 2 PAd 2 ) 2 and IrH 2 Cl[HN(CH 2 CH 2 P i Pr 2 ) 2 ](complex 2) were purchased from Strem and used as received. Poly(propylene carbonate) (M w = 100,698, M w /M n = 1.77, carbonate linkage > 99%) was received as a gift from Prof. Xiao-Bing Lu at Dalian University of Technology. D 2 (99.99%) was purchased from Peric Gas Co., Ltd., China. 2. General procedure for the synthesis of Ru complexes 1a-1e and 3 a) Preparation of Ru complex 1a [4] To a 100 ml Schlenk tube were added HCl HN(CH 2 CH 2 PPh 2 ) 2 (1.20 g, 2.51 mmol), toluene (20 ml), and 15% aqueous NaH solution (10 ml) under an Ar atmosphere. The resulting mixture was stirred at room temperature until the solid disappeared. After phase separation, the organic layer was washed twice with distilled water (5 ml), and the combined aqueous layer was extracted twice with toluene (2 10 ml). The combined organic phase was dried over anhydrous Na 2 S 4, filtered, and the solvent was removed under vacuum to afford the crude amine product HN(CH 2 CH 2 PPh 2 ) 2 as a thick yellowish oil. The crude amine, without further

4 purification, was dissolved in toluene (18 ml), followed by addition of RuHCl(C)(PPh 3 ) 3 (2.28 g, 2.39 mmol) under an Ar atmosphere. The resultant mixture was heated to reflux for 2 h. After being cooled to rt, the solution was diluted with hexane (10 ml), and the precipitate was filtered. The pale yellow solid thus obtained was washed with hexane (5 ml), then dried under vacuum g, 97% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 8H), (m, 12H), 4.36 (s, br, 1H), (m, 2H), (m, 2H), (m, 4H), (t, J = 19.6 Hz, 1H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 52.6 (d, J = 18.1 Hz) ppm; HRMS (MALDI) m/z calcd. for [C 29 H 28 NP 96 2 Ru] + : , Found: [M-H 2 -Cl] +, IR (film) 1972, 1904 cm -1. b) Typical procedure for the preparation of Ru complexes 1b-e and 3 A mixture of HN(CH 2 CH 2 P i Pr 2 ) 2 (217 mg, mmol) and RuHCl(C)(PPh 3 ) 3 (644 mg, mmol) in degassed toluene (4 ml) was heated to reflux for 5 h. After being cooled to room temperature, the mixture was diluted with hexane (6 ml). The resulting pale yellow solid was collected by filtration and then dried under vacuum. 288 mg, 90% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 2H), (m, 6H), (m, 2H), (m, 6H), (m, 18H), (t, J = 19.2 Hz, 0.12H), (t, J = 18.0 Hz, 0.88H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 74.6 (s, br) ppm; HRMS (MALDI) m/z calcd. for [C 17 H 38 NP 96 2 Ru] + : , Found: [M-Cl] + ; IR (film) 1973, 1960, 1910 cm -1. RuHCl(C)[(tBu 2 PCH 2 CH 2 ) 2 NH] (1c): 85% yield, pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 6.44 (br s, 1H), (m, 0.9H), (m, 2.1H), (m, 2.1H), (m, 0.9H), (m, 4H), (m, 36H), (t, J = 19.4 Hz, 0.6), (t, J = 18.4 Hz, 0.4 H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 89.0 (d, J = 9.1 Hz), 87.6 (s) ppm; HRMS (MALDI) m/z calcd. for [C 21 H 46 NP 96 2 Ru] + : , Found: [M-Cl] + ; IR (film) 1897 cm -1.

5 RuHCl(C)[(Cy 2 PCH 2 CH 2 ) 2 NH] (1d): 98% yield, pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 48H), (br s, 1H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 65.2 (s), 47.6 (s) ppm; HRMS (MALDI) m/z calcd. for [C 29 H 54 NP 96 2 Ru] + : , Found: [M-Cl] + ; IR (film) 1910 cm -1. RuHCl(C)[(Ad 2 PCH 2 CH 2 ) 2 NH] (1e): 92% yield, pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.49 (br s, 1H), (m, 2H), (m, 66H), (t, J = 15.6 Hz, 1H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 84.4 (d, J = 9.2 Hz) ppm; HRMS (MALDI) m/z calcd. for [C 45 H 70 NP 96 2 Ru] + : , Found: [M-Cl] + ; IR (film) 1914 cm -1. Me Ph Cl Ph P N Ru C P Ph H Ph 3 RuHCl(C)[(Ph 2 PCH 2 CH 2 ) 2 NMe] (3): 98% yield, pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 8H), (m, 12H), (m, 0.6H), (m, 7.4H), 2.53 (s, 2H), 2.35 (s, 1H), (t, J = 19.6 Hz, 0.3H), (t, J = 19.6 Hz, 0.7H) ppm; 31 P NMR (161.9 MHz, CDCl 3 ) δ 54.4 (s), 49.5 (d, J = 6.3 Hz) ppm; HRMS (MALDI) m/z calcd. for [C 30 H 30 NP 96 2 Ru] + : , Found: [M-H 2 -Cl] + ; IR (film) 1975, 1903 cm General procedure for the preparation of cyclic carbonates [5] A 125 ml Parr autoclave equipped with a stirring bar was charged with nbu 4 NBr (64 mg, 0.20 mmol), ZnBr 2 (45 mg, 0.20 mmol) and the epoxide (160 mmol), then sealed. The reaction vessel was purged three times with C 2 and finally pressurized with C 2 to 40 atm. The vessel was heated at 140 C (bath temperature) for 3-10 h with stirring. After being cooled to room temperature, the reaction mixture was purified by distillation or recrystallization.

6 4-ethyl-1,3-dioxolan-2-one [6] : colorless oil, 95% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 1H), (m, 2H), 1.04 (t, J = 7.6 Hz, 3H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.8, 78.0, 69.1, 26.9, 8.6 ppm. nbu 4-butyl-1,3-dioxolan-2-one [7] : colorless oil, 98% yield. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 1H), 4.53 (t, J = 7.8 Hz, 1H), 4.08 (t, J = 7.8 Hz, 1H), (m, 2H), (m, 4H), 0.93 (t, J = 6.6 Hz, 3H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.9, 76.9, 69.2, 33.1, 26.1, 21.9, 13.4 ppm. Bn 4-benzyl-1,3-dioxolan-2-one [7] : colorless oil, 96% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 4.44 (dd, J = 8.4 Hz, 8.0 Hz, 1H), 4.18 (dd, J = 8.4 Hz, 6.8 Hz, 1H), 3.17 (dd, J = 14.0 Hz, 6.0 Hz, 1H), 2.99 (dd, J = 14.0 Hz, 6.8 Hz, 1H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.7, 133.9, 129.2, 128.7, 127.2, 76.7, 68.3, 39.2 ppm. Ph 4-phenyl-1,3-dioxolan-2-one [7] : white solid, 87% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 5.68 (t, J = 8.0 Hz, 1H), 4.81 (t, J = 8.0 Hz, 1H), 4.35 (t, J = 8.0 Hz, 1H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.8, 135.6, 129.4, 129.0, 125.7, 77.8, 71.0 ppm. Bn 4-(benzyloxymethyl)-1,3-dioxolan-2-one [8] : colorless oil, 89% yield. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 4.59 (q, J = 11.6 Hz, 2H), 4.47 (t, J = 8.4 Hz, 1H), 4.37 (dd, J = 8.2 Hz, 6.0 Hz, 1H), 3.71 (dd, J = 11.2 Hz, 3.6 Hz, 1H), 3.61 (dd, J = 10.8 Hz, 3.6 Hz,

7 1H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.9, 137.0, 128.2, 127.6, 127.3, 74.9, 73.1, 68.6, 65.9 ppm. 4,5-dimethyl-1,3-dioxolan-2-one [9] : colorless oil, 77% yield. cis/trans = 2.8/1 by 1 H NMR. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H, cis), (m, 2H, trans), (m, 6H, trans), (m, 6H, cis) ppm; 13 C NMR (100MHz, CDCl 3 ) δ (cis), (trans), 79.7 (trans), 75.8 (cis), 17.9 (trans), 14.0 (cis) ppm. 4,4-dimethyl-1,3-dioxolan-2-one [10] : colorless oil, 75% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 4.16 (s, 2H), 1.53 (s, 6H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 154.3, 81.6, 75.1, , ppm. 4,4,5,5-tetramethyl-1,3-dioxolan-2-one [11] : + H H KtBu THF, 140 o C + H H To a solution of pinacol (11.8 g, 100 mmol) and ethylene carbonate (10 g, 114 mmol) in THF (20 ml) in an autoclave, was added potassium tert-butoxide (30 mg, 0.27 mmol). The reaction mixture was heated at 140 C (bath temperature) for 20 h, and then cooled to room temperature. The resulting white solid was collected by filtration and washed with THF, then dried under vacuum. 9.8 g, 68% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 1.41 (s, 12H) ppm; 13 C NMR (100MHz, CDCl 3 ) δ 153.7, 85.9, 22.1 ppm. 4. General procedure for the hydrogenation of cyclic carbonates (a) Substrate/Catalyst molar ratios at 1000/1~5000/1: In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol, s/c= 1000), KtBu (3.2 mg, mmol, s/b= 1000), THF (20 ml) and ethylene carbonate (2.52 g, 28.6 mmol). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The vessel was heated at 140 C (bath temperature) for 0.5 h with stirring, and then cooled in an ice-water bath for 1.5 h. The residual H 2 was released carefully in a hood and the mixture was analyzed by GC with p-xylene as the internal standard.

8 GC conditions: DM-wax column, carrier gas: N 2, Injection temp.: 250 C, Detector temp.: 300 C, flow rate: 1 ml/min, oven temp.: 40 C, 1 min, 10 C/min, 230 C, 30 min. (b) Substrate/Catalyst molar ratios at 10000/1: A stock solution of KtBu ( mmol/ml) was prepared by dissolving KtBu (1.3 mg, mmol) in THF (20 ml). A 125-mL Parr autoclave was charged with Ru complex 1a (1.7 mg, mmol), KtBu stock solution (5 ml, mmol), THF (15 ml) and ethylene carbonate (2.52 g, 28.6 mmol) in a glove box. p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for 48 h with stirring, and then cooled in an ice-water bath for 1.5 h. H 2 was released carefully in a hood and the mixture was analyzed by GC with p-xylene as the internal standard. (c) Substrate/Catalyst molar ratios at /1: A stock solution of KtBu ( mmol/ml) was prepared by dissolving KtBu (1.3 mg, mmol) in THF (20 ml). A stock solution of Ru complex 1a ( mmol/ml) was made by dissolving Ru complex 1a (1.7 mg, mmol) in THF (15 ml), followed by addition of the KtBu stock solution (5 ml, mmol). A 125-mL Parr autoclave was charged with the freshly prepared Ru complex 1a stock solution (2 ml, mmol), THF (18 ml) and ethylene carbonate (2.52 g, 28.6 mmol) in a glove box. p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm and the reaction vessel was heated at 140 C (bath temperature) for 72 h with stirring, and then cooled in an ice-water bath for 1.5 h. The residual H 2 was released carefully in a hood and the mixture was analyzed by GC with p-xylene as the internal standard. Analytical data of the diols H H nbu hexane-1,2-diol [12] : colorless oil, 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), (m, 6H), (m, 3H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 72.3, 66.7, 32.7, 27.7, 22.7, 13.9 ppm. H H Bn 3-phenylpropane-1,2-diol [13] : colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 137.9, 129.2, 128.3, 126.2, 73.0, 65.5, 39.4 ppm.

9 H H Ph 1-phenylethane-1,2-diol [12] : white solid. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 140.5, 128.4, 127.8, 126.1, 74.7, 67.9 ppm. Me H H 3-methoxypropane-1,2-diol [14] : colorless oil. 1 H NMR (400 MHz, CD 3 D) δ (m, 1H), (m, 2H), (m, 2H), 3.36 (s, 3H) ppm; 13 C NMR (100 MHz, CD 3 D) δ 75.1, 72.0, 64.4, 59.4 ppm. H Bn H 3-(benzyloxy)propane-1,2-diol [15] : colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 4.55 (s, 2H), (m, 1H), (m, 4H), 2.78 (br s, 1H), 2.30 (br s, 1H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 137.6, 128.3, , , 73.3, 71.4, 70.8, 63.8 ppm. H butane-2,3-diol [16] : colorless oil. cis/trans = 1/1.3; 1 H NMR (300 MHz, CD 3 D) δ (m, 2H, cis isomer), (m, 2H, trans isomer), (m, 2H), (m, 6H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 72.2, 70.7, 19.0, 16.7 ppm. H H H 2-methylpropane-1,2-diol [17] : colorless oil. 1 H NMR (400 MHz, CD 3 D) δ 4.61 (br s, 2H), 1.16 (s, 6H) ppm; 13 C NMR (100 MHz, CD 3 D) δ 71.8, 71.6, 26.0 ppm. 5. Complementary reaction optimization data Table S1: Solvent effect on the 1a-catalyzed hydrogenation of 4-methyl-1,3-dioxolan-2-one. [a] 0.1 mol% 1a 0.1 mol% KtBu H + H 2 solvent (20 ml), 2 h 50 atm 100 o C H + MeH Entry solvent Conv. [%] [b] Yield (diol) [%] [b] Yield (MeH) [%] [b] 1 THF dioxane PhCH [c] MeH \ 5 [d] EtH

10 [a] Substrate: 28.6 mmol. [b] Determined by GC analysis using p-xylene (50 μl) as the internal standard. [c] Dimethyl carbonate (ca. 10%) was detected. [d] Significant amount of ethyl formate and diethyl carbonate were detected. Table S2: Effect of THF volumes on the 1a-catalyzed hydrogenation of 4-methyl-1,3-dioxolan-2- one. [a] 0.1 mol% 1a H 1 mol% KtBu + H 2 + THF, 100 o H MeH 50 atm C, 20 h Entry V THF (ml) Conv. [%] [b] Yield (diol) [%] [b] Yield (MeH) [%] [b] > [a] Substrate: 28.6 mmol. [b] Determined by GC analysis using p-xylene (50 μl) as the internal standard. Table S3: Effect of KtBu quantities (x molar equivalents relative to that of 1a) on 1a-catalyzed hydrogenation of 4-methyl-1,3-dioxolan-2-one. [a] + H mol% 1a x eq. KtBu to 1a 50 atm THF (20 ml), 100 o C 2 h H H + MeH Entry KtBu [x] Conv. [%] [b] Yield (diol) [%] [b] Yield (MeH) [%] [b] [a] Substrate: 28.6 mmol. [b] Determined by GC analysis using p-xylene (50 μl) as the internal standard.

11 Conversion [%] Base Effect Base eq. to Ru Table S4: The effect of hydrogen pressure on 1a-catalyzed hydrogenation of 4-methyl-1,3- dioxolan-2-one [a] + H mol% 1a 0.1 mol% KtBu THF (20 ml), 100 o C 2 h H H + MeH Entry ph 2 (atm) Conv. [%] [b] Yield (diol) [%] [b] Yield (MeH) [%] [b ] [a] Substrate: 28.6 mmol. [b] Determined by GC analysis using p-xylene (50 μl) as the internal standard. Table S5: The effect of reaction temperature on 1a-catalyzed hydrogenation of 4-methyl-1,3- dioxolan-2-one [a] 0.1 mol% 1a 0.1 mol% KtBu H + H 2 + H MeH THF (20 ml), 2 h 50 atm Entry T ( o C) Conv. [%] [b] Yield (diol) [%] [b] Yield (MeH) [%] [b] > [a] Substrate: 28.6 mmol. [b] Determined by GC analysis using p-xylene (50 μl) as the internal standard. 6. Hydrogenative depolymerization of poly(propylene carbonate) (PPC) to methanol and propylene glycol In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (15.8 mg,

12 mmol, s/c= 1000), KtBu (2.9 mg, mmol, s/b= 1000), THF (25 ml) and poly(propylene carbonate) [M w = 100,698 (M w /M n = 1.77), > 99% carbonate linkage] (2.69 g, 26.0 mmol). p- Xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for 24 h with stirring, and then cooled in an ice-water bath for 1.5 h. H 2 was released carefully in a hood and the mixture was analyzed by GC with p-xylene as the internal standard. 7. Deuteration of ethylene carbonate and tetramethylethylene carbonate (a) Deuteration of ethylene carbonate: In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol, s/c= 1000), KtBu (3.2 mg, mmol, s/b = 1000), THF (20 ml) and ethylene carbonate (2.52 g, 28.6 mmol). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for 0.5 h with stirring, and then cooled in an ice-water bath for 1.5 h. The residual D 2 was carefully released in a hood and the mixture was analyzed by GC with p-xylene as the internal standard. To determine the deuterium content of the deuterium-labelled products, the resulting methanol and ethylene glycol were further converted to methyl benzoate and ethylene dibenzoate, respectively. To the crude reaction mixture (2 ml) was added pyridine (0.83 ml) and benzoyl chloride (1.19 ml) at 0 C, and the resulting mixture was stirred at room temperature for 5 h. The solvent was removed under vacuum. The residual was purified by column chromatography on silic gel using a mixture of petroleum ether and ethyl acetate (50/1 ~ 30/1) as the eluent, to afford methyl benzoate and ethylene dibenzoate, respectively. The deuterium incorporation was determined by 1 H-NMR analysis. (b) Deuteration of tetramehylethylene carbonate: A 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol), KtBu (3.2 mg, mmol), THF (20 ml) and ethylene carbonate (4.12 g, 28.6 mmol) in a glove box. p-xylene (50 μl) was added to the reaction mixture as the internal standard. The reaction vessel was sealed and purged three times with D 2 gas. The pressure of D 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) with stirring for 24 h, and then cooled in ice water for 1.5 h. D 2 was released carefully in a safety hood and the yields of products were analyzed by GC. The deuterium content of the methanol at the carbon atom is determined as follows. To the crude reaction mixture (2 ml) were added pyridine (0.28 ml) and benzoyl chloride (0.40 ml) at 0 ºC. The mixture was stirred at room temperature for 5 h. The solvent was

13 removed under vacuum and the residual was purified by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (50/1) as eluent to afford methyl benzoate. The deuterium incorporation at carbon atom of the deuterated methanol was determined by 1 H- NMR analysis of its benzoate derivative. (c) Deuteration of ethylene glycol: In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol, s/c= 1000), KtBu (3.2 mg, mmol, s/b= 1000), THF (20 ml) and ethylene glycol (1.78 g, 28.6 mmol). The reaction vessel was sealed and purged three times with D 2 gas. The pressure of D 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) with stirring for 0.5 h with stirring, and then cooled in ice water for 1.5 h. D 2 was released carefully in a hood. To determine the deuterium content in alkyl backbone of ethylene glycol, this was converted to ethylene dibenzoate, and then analyzed by 1 H NMR. 8. Catalytic hydrogenation of (R)-propylene carbonate In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol, s/c= 1000), KtBu (3.2 mg, mmol, s/b= 1000), THF (20 ml) and (R)-propylene carbonate (2.92 g, 28.6 mmol, >99% ee). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for1 h, and then cooled in an ice-water bath for 1.5 h. The residual H 2 was released carefully in a hood, and the mixture was analyzed by GC with p-xylene as the internal standard. To determine the optical purity of the 1,2-propanediol product, this was converted to 2,2,4- trimethyl-1,3-dioxolane by using the following procedure: a portion of the crude reaction mixture (ca. 1 ml) was concentrated in vaccum. The residual was dissolved in acetone (ca. 1 ml), then pyridinium p-toluenesulfonate (PPTS) (ca. 2 mg) was added. The mixture was stirred at room temperature for 1 h, and then analyzed directly by chiral GC. GC conditions for determination of enantiomeric excess of propylene carbonate: Supelco BATA- DEX TM 120 column, carrier gas: N 2 ; injection temp.: 250 C, detector temp.: 300 C, flow rate: 0.6 ml/min, oven temp.: 95 C. GC conditions for determination of enantiomeric excess of 1,2-propanediol: Supelco GAMMA- DEX TM 225 column, carrier gas: N 2 ; injection temp.: 250 C, detector temp.: 300 C, flow rate: 0.6 ml/min, oven temp.: 60 C. 9. Catalytic racemization of (R)-1,2-propanediol (a) Under H 2 atmosphere: In a glove box, a 125-mL Parr autoclave was charged with Ru

14 complex 1a (8.7 mg, mmol, s/c= 1000), KtBu (1.6 mg, mmol, s/b= 1000), THF (10 ml) and (R)-1,2-propanediol (1.09 g, 14.3 mmol, 95% ee). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for 1 h, and then cooled in ice water for 1.5 h. H 2 was released carefully in a hood, and the mixture was analyzed by GC with p-xylene as the internal standard. For determination of the enantiomeric excess of 1,2- propanediol, it was converted to 2,2,4-trimethyl-1,3-dioxolane by using the following procedure: a portion of the crude reaction mixture (ca. 1 ml) was concentrated in vaccum to dryness. The residual was dissolved in acetone (ca. 1 ml), then pyridinium p-toluenesulfonate (PPTS) (ca. 2 mg) was added. The mixture was stirred at room temperature for 1 h. The reaction mixture was analyzed directly by GC. GC conditions for determination of enantiomeric excess of 2,2,4- trimethyl-1,3 -dioxolane: Supelco GAMMA-DEX TM 225 column, carrier gas: N 2 ; injection temp.: 250 C, detector temp.: 300 C, flow rate: 0.6 ml/min, oven temp.: 60 C. (b) Under N 2 atmosphere: In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (8.7 mg, mmol, s/c= 1000), KtBu (1.6 mg, mmol, s/b= 1000), THF (10 ml) and (R)-1,2-propanediol (1.09 g, 14.3 mmol, 95% ee). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and heated at 140 C (bath temperature) for 1 h, and then cooled in ice water for 1.5 h. The mixture was analyzed by GC with p-xylene as the internal standard. For determination of the enantiomeric excess of the 1,2-propanediol, it was converted to 2,2,4-trimethyl-1,3-dioxolane by using the following procedure: a portion of the crude reaction mixture (ca. 1 ml) was concentrated in vaccum to dryness. The residual was dissolved in acetone (ca. 1 ml), then pyridinium p- toluenesulfonate (PPTS) (ca. 2 mg) was added. The mixture was stirred at room temperature for 1 h. The reaction mixture was analyzed directly by GC. GC condition for determination of enantiomeric excess of 2,2,4-trimethyl-1,3-dioxolane: Supelco GAMMA-DEXTM 225 column, carrier gas: N 2 ; injection temp.: 250 C, detector temp.: 300 C, flow rate: 0.6 ml/min, oven temp.: 60 C. 10. Control Experiments Catalytic hydrogenation of Paraformaldehyde In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (17.4 mg, mmol, s/c= 1000), KtBu (3.2 mg, mmol, s/b= 1000), THF (20 ml) and Paraformaldehyde (0.858 g, 28.6 mmol of the oxymethylene units). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged

15 three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The reaction vessel was heated at 140 C (bath temperature) for 2 h, and then cooled in ice water for 1.5 h. The residual H 2 was released carefully in a hood, and the mixture was analyzed by GC with p-xylene as the internal standard. 2-hydroxyhexyl formate A and 1-hydroxyhexan-2-yl formate B nbu + HC 2 H 80 o C 5 h nbu R 2 R 1 A R 1 = CH, R 2 = H B R 1 = H, R 2 = CH A mixture of 2-butyloxirane (20 ml, 166 mmol) and formic acid (7.5 ml, 199 mmol) was heated at 80 C for 5 h. After being cooled to room temperature, the reaction mixture was neutralized with sodium bicarbonate to ph = 7~8. The mixture was extracted with diethyl ether (20 ml 3). The combined organic phase was dried over anhydrous sodium sulfate, then filtered. After removal of the solvent by vacuum evaporation, the residue was purified by column chromatography on silic gel using a mixture of petroleum ether and ethyl acetate (10/1 ~ 5/1) as the eluent, to afford 2-hydroxyhexyl formate and 1-hydroxyhexan-2-yl formate as a 2/1 isomeric mixture. Colorless oil, 11.8 g, yield 49%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.15 (s, 1H, minor isomer), 8.13 (s, 1H, major isomer), (m, 1H, minor isomer), (m, 1H, major isomer), (m, 1H, major isomer), (m, 1H, major isomer), (m, 1H, minor isomer), (m, 1H, minor isomer), (m, 1H, major isomer), (m, 1H, minor isomer), (m, 6H), (m, 3H) ppm; 13 C NMR (100MHz, CDCl 3 ) δ (minor isomer), (major isomer, 75.5 (minor isomer), 69.6 (major isomer), 68.0 (major isomer), 64.3 (minor isomer), 32.9 (major isomer), 30.0 (minor isomer), 27.4 (major isomer), 27.3 (minor isomer), 22.5 (major isomer), 22.4 (minor isomer), 13.9 (major isomer), 13.8 (minor isomer) ppm; HRMS (EI) m/z calcd. for C 6 H 12 2 : , Found: [M- CH 2 ] +. Control experiment: catalytic hydrogenation of a 1:1 mixture (molar ratio) of 4-butyl-1,3- dioxolan-2-one and hydroxyhexyl formates (2-hydroxyhexyl formate and 1- hydroxyhexan-2-yl formate, A/B = 2:1) In a glove box, a 125-mL Parr autoclave was charged with Ru complex 1a (8.7 mg, mmol), KtBu (1.6 mg, mmol), THF (20 ml), the isomeric mixture of 2-hydroxyhexyl formate (A) and 1-hydroxyhexan-2-yl formate (B) (molar ratio A/B = 2/1) (2.08 g, 14.3 mmol) and 4-butyl-1,3-dioxolan-2-one (2.06 g, 14.3 mmol). p-xylene (50 μl) was added to the reaction mixture as an internal standard. The reaction vessel was sealed and then purged three times with hydrogen gas. The pressure of H 2 in the autoclave was finally adjusted to 50 atm. The

16 reaction vessel was heated at 140 C (bath temperature) for 0.5 h, and then cooled in ice water for 1.5 h. H 2 was released carefully in a hood, and the mixture was analyzed by GC with p- xylene as the internal standard.

17 11. GC charts of the hydrogenation reaction products

18

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21

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25 12. NMR spectra of the catalysts and products

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34 References [1] N. Ahmad, J. J. Levison, S. D. Robinson, M. F. Uttley, Inorg. Synth. 1974, 15, 45. [2] R. G. Nuzzo, S. L. Haynie, M. E. Wilson, G. M. Whitesides, J. rg. Chem. 1981, 46, [3] D. S. McGuinness, P. Wasserscheid, D. H. Morgan, J. T. Dixon, rganometallics 2005, 24, 552. [4] W. Kuriyama, T. Matsumoto,. gata, Y. Ino, K. Aoki, S. Tanaka, K. Ishida, T. Kobayashi, N. Sayo, T. Saito, rg. Process Res. Dev. 2012, 16, 166. [5] H. Xie, S. Li, S. Zhang, J. Mol. Catal. A: Chem., 2006, 250, 30. [6] Y. -M. Shen, W. -L. Duan, M. Shi, Eur. J. rg. Chem. 2004, 14, [7] R. L. Paddock, S. T. Nguyen, Chem. Commun. 2004, [8] S. G. Davies, A. M. Fletcher, W. Kurosawa, J. A. Lee, G. Poce, P. M. Roberts, J. E. Thomson, D. M. Williamson, J. rg. Chem. 2010, 75, [9] T. Iida, T. Itaya, Tetrahedron 1993, 49, [10] A. Baba, T. Nozaki, H. Matsuda, Bull. Chem. Soc. Jpn. 1987, 60, [11] M. Suzuki, T. Sugai Bull. Chem. Soc. Jpn. 2004, 77, [12] K. C. Nicolaou, S. A. Snyder, D. A. Longbottom, A. Z. Nalbandian, X. Huang, Chem. Eur. J. 2004, 10, [13] A. Wang, H. Jiang, J. rg, Chem. 2010, 75, [14] J. I. Garcia, H. Garcia-Marin, J. A. Mayoral, P. Perez, Green Chem. 2010, 12, 426. [15] D. M. Dishong, C. J. Diamond, M. I. Cinoman, G. W. Gokel, J. Am. Chem. Soc. 1983, 105, 586. [16] D. Enders, S. Nakai, Chem. Ber. 1991, 124, 219. [17] E. L. Eliel, C. Herrmann, J. T. Traxler, J. Am. Chem. Soc. 1956, 78, 1193.