Folding-Driven Asymmetric Induction of a Catalytic Dendrimer

Supporting Information Folding-Driven Asymmetric Induction of a Catalytic Dendrimer Jianfeng Yu, T.V. RajanBabu* and Jon R. Parquette* Department of Chemistry, The hio State University100 W. 18 th Ave. Columbus, hio 43210 Table of Contents Details of dendrimers synthesis for catalyst C1 C5 S2 S17 ydrogenation reaction and product analysis S17 Literature references S18 1 MR, 13 C and 31 P MR of all new compounds S19-S51 Figure 1. Chiral information propagates from the dendron terminal groups to the catalytic center via the biphenyl core, which serves to relay the chirality to the catalytic site via its axial chriality S1

Scheme 1 a PPh 2 PPh 2 b Ph Ph P P Rh SbF 6 Ph Ph C 1 R 1 d R 1 R 1 R 1 f Bn Bn c R 1 = R 1 = MM e R 1 = MM R 1 = SI 1 R 1 d R 1 R 1 R 1 f Bn Bn c R 1 = R 1 = MM e R 1 = MM R 1 = (R), (S)-SI 2 2 h, i j g R 2 R 2 = R 2 = Cl 2 Me SI 3 Me 2 C k 2 R l R R R = Me R = i-pr SI 4 R = Me SI 5 R = i-pr SI 6 key. a. Ph 2 PCl, DMAP, TF; b. Rh(CD) 2 SbF 6, C 2 Cl 2 ; c. a, MM-Cl, TF; d. n-buli, TMEDA, 1,2-dibromotetrachloroethane, TF/benzene; e. ai, TMSCl, C 2 Cl 2 /C 3 C; f. K 2 C 3, benzyl bromide, DMF; g. oxalyl chloride, DMF, C 2 Cl 2 ; h. (S)-(+)-methoxy-2-propanol, Et 3, C 2 Cl 2 ; i. Pd/C, 2 ; j. 4-bromopyridine-2,6-dicarbonyl dibromide, Et 3, C 2 Cl 2 ; K. L-alanol(or L-valinol), ZnCl 2, chlorobenzene; l. 4-bromopyridine-2,6-dicarbonyl dibromide, pyridine, DMAP, C 2 Cl 2. S2

Scheme 2 Me Me Me Me Me Me Me Me SI 1 a, b Bn c d PPh 2 e Bn PPh 2 Ph 2 P Rh P Ph 2 SbF 6 Me Me Me Me Me Me Me Me SI 7 SI 8 SI 9 C 2 SI 1 R R a, b Bn c d PPh 2 e Bn PPh 2 R R R R R R R R R R Ph 2 P R R Rh SbF P 6 Ph 2 R R R = Me, SI 10; R = i-pr, SI 11 R = Me, SI 12; R = i-pr, SI 13 R = Me, SI 14; R = i-pr, SI 15 R = Me, C3; R = i-pr, C4 (R)-SI 2 a, b Bn Bn c d PPh 2 PPh 2 e Ph 2 P Rh P Ph 2 SbF 6 SI (R)-16 SI (R)-17 SI (R)-18 C5 key. a. n-buli, TMEDA, B(Me) 3, TF; b. SI 3(SI 5 or SI 6), Pd(PPh 3) 4, a 2C 3, DME/ 2; c. Pd/C, 2; d. Ph 2PCl, DMAP, TF; e. Rh(CD) 2SbF 6. S3

Figure 2. 31 P MR of phosphinite precursors to C1 C5 General Methods Melting points were determined in open capillaries and are uncorrected. 1 MR, 13 C MR, and 31 P MR spectra were recorded on a uker AC-250, 400 or 500 instruments as indicated. UV-Vis spectra were recorded on a P8452A instrument. EI or FAB mass spectra were recorded at the MS instrument in The hio-state University Chemical Instrument Center.Chemistry. MALDI-TF spectrometry was performed using 2,5-dihydroxybenzoic acid as the matrix in TF and recorded on uker Microflex instrument at Chemistry Department of The hio-state University. Circular dichroism (CD) measurements were carried out on an Aviv 202 CD spectrometer, using optical grade solvents and quartz glass curettes with a 10 mm path length. All reactions were performed under a nitrogen atmosphere. Tetrahydrofuran (TF) and diethyl ether was distilled from sodium/benzophenone; dichloromethane, pyridine and triethylamine (Et 3 ) were distilled from calcium hydride. Chromatographic separations were performed on silica gel 60 (230 240 mesh, 60A) using the indicated solvents. Bn Bn 2,2 -Bis(benzyloxy)-3,3 -dibromobiphenyl (SI 1). To a solution of 3,3 -dibromobiphenyl-2,2 -diol [1] (1.43 g, 4.15 mmol) in dry DMF (18 ml), K 2 C 3 (2.3 g,16.6 mmol) was added, followed by benzyl S4

bromide (2.14 g, 1.5 ml, 12.5 mmol). The mixture was heated to 70 o C and stirred for 20 h. After cooling to room temperature, the solution was filtered with a short column, evaporation of DMF by Kugelrohr, the residue was purified by flash chromatography on silica gel using 95:5 (v/v) hexanes:etac to give product as white solid (2.11 g, 97%). M.p.96 98 o C. 1 -MR(400Mz, CDCl 3 ): δ 4.84 p.p.m.(s, 4), 7.14 (t, J = 7.6 z, 2), 7.26 7.24 (m, 4), 7.39 7.37 (m, 6), 7.44 (dd, J = 7.6, 1.6 z, 2), 7.75 (dd, J = 8.0, 1.6 z, 2). 13 C-MR (100 Mz, CDCl 3 ): δ 136.38, 133.52, 133.21, 130.84, 128.16, 128.14, 127.90, 124.99, 118.00, 74.78. RMS(m/z): [M+K] + calcd for C 26 20 2 K 2, 560.9467; found, 560.9460. Bn Bn (R)-2,2'-bis(benzyloxy)-3,3'-dibromo-1,1'-binaphthyl (SI 2). To a solution of (R)-3,3'-dibromo-1,1'-binaphthyl-2,2'-diol [2] (1.2 g, 2.7 mmol) in DMF (12 ml), K 2 C 3 (1.5 g, 10.8 mmol) was added, followed by benzylbromide (1.39 g, 0.96 ml, 8.1 mmol). The mixture was heated to 70 o C and stirred for 20 h. After cooling to room temperature, filtration with a short column, and evaporation of DMF with Kugelrohr, the residue was purified by flash chromatography on silica gel using 75:25 (v/v) hexanes: C 2 Cl 2 to give product as white solid (1.58 g, 94%). M.p..124 126 o C; 1 MR (400 Mz, CDCl 3 ): δ 4.70 p.p.m. (d, J = 10.4 z, 2), 5.08 (d, J = 10.4 z, 2), 6.96 6.94 (m, 4), 7.24 (m, 6), 7.31 7.29 (m, 2), 7.38 (t, J = 7.6 z, 2), 7.52 (t, J = 7.6 z, 2), 7.92 (d, J = 8.4 z, 2), 8.39 (s, 2). 13 C-MR (100 Mz, CDCl 3 ): δ 151.65, 136.59, 133.07, 132.89, 131.49, 127.94, 127.65, 127.60, 127.12, 127.08, 126.89, 125.90, 117.73, 75.03. MALDI(m/z): [M+a] + calcd for C 34 24 2 2 a +, 645.004; found, 645.032. Me Me (S)-Ether G1 dendron bromide (SI 3). To a stirred mixture of (S)-1-methoxypropan-2-yl-2-aminobenzoate [3] (1.0 g, 4.8 mmol), Et 3 (0.66 ml, 5 mmol), and activated 4A molecular sieves (0.5 g) in C 2 Cl 2 (30 ml), a solution of 4-bromopyridine-2,6-dicarbonyl dibromide (0.85 g, 2.3 mmol) in C 2 Cl 2 (20 ml) was added dropwise via a syringe over 30 min at 0 o C. The mixture was stirred at room temperature for 2 h, then filtered and concentrated. Residue was purified by flash purified by chromatography on silica gel using 80:20 (v/v) hexanes:etac, affording the product as white solid (1.33 g, 92%). M.p..94 96 o C; 1 -MR (400 Mz, CDCl 3 ): δ 1.11 p.p.m. (d, J = 6.4 z, 6), 3.18 S5

(s, 6), 3.30 (dd, J = 10.5, 4.2 z, 2), 3.36 (dd, J = 10.6, 5.7 z, 2), 4.96 4.92 (m, 2), 7.18 (td, J = 7.4, 1.0 z, 2), 7.61 (td, 7.8, 1.5 z, 2), 8.06 (dd, J = 7.9, 1.5 z, 2), 8.56 (s, 2), 8.62(d, J = 7.8 z, 2), 12.68 (s, 2). 13 C-MR (100 Mz, CDCl 3 ): δ 166.61, 160.97, 150.32, 139.84, 136.53, 134.10, 131.08 128.40, 123.74, 121.90, 118.46, 74.58, 70.35, 58.93, 16.31. RMS (m/z): [M+a] + calcd for C 29 30 3 8 a +, 650.1114; found, 650.1151. 2 (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)benzenamine (SI 4) [4] To a solution of 2-aminobenzonitrile (3.0 g, 25.4 mmol) in chlorobenzene (50 ml), ZnCl 2 (3.46 g, 25.4 mmol) and L-valinol (2.64 g, 25.6 mmol) were added, respectively. The mixture was heated to 130 o C for 36 h. After cooling to room temperature, 2 (10 ml) was added, the organic layer was separated and the aqueous layer was extracted with C 2 Cl 2 (3 10 ml), the combined organic extracts were washed with water, brine, dried over MgS 4. After filteration, the solution was concentrated and then purified by flash chromatography on silica gel using 95:5 (v.v) hexanes:etac affording the product as white solid (3.89 g, 75%). M.p.. 68 70 o C 1 -MR (500 Mz, CDCl 3 ): δ 0.93 p.p.m. (d, J = 6.7 z, 3), 1.01 (d, J = 6.5 z, 3), 1.79 1.75 (m, 1), 3.99 (t, J = 8.0 z, 1), 4.10 4.07 (m, 1), 4.32 4.28 (m, 1), 6.12 (s, 2), 6.64 (td, J = 7.0, 1.0 z,1), 6.68 (d, J = 8.0 z, 1), 7.18 (td, J = 7.5, 1.5 z, 1), 7.67 (dd, J = 8.0, 2.0, 1). 13 C-MR (125.7 Mz, CDCl 3 ): δ 163.50, 148.58, 131.86, 129.54, 115.93, 115.58, 109.14, 72.86, 68.71, 33.15, 18.92, 18.56. RMS (m/z): [M+] + calcd for C 12 17 2 +, 205.1341; found, 205.1324. C 3 3 C 4-omo- 2, 6 -bis(2-((s)-4-methyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide(si 5) To a stirred solution of (S)-2-(4-methyl-4,5-dihydrooxazol-2-yl)benzenamine [5, 6] (0.16 g, 0.92 mmol) in C 2 Cl 2 (8 ml) and pyridine (1 ml) with activated 4 Å molecular sieves, a solution of 4-bromopyridine- 2,6-dicarbonyl dibromide (0.17 g, 0.45 mmol) in C 2 Cl 2 (2 ml) was added at 0 o C over 20 min. The mixture was stirred at room temperature for 12 h, then filtered to remove molecular sieves and concentrated, and the pyridine was evaporated. The resulting residue was purified by flash chromatography on silica gel using 90:10 (v/v) hexanes:etac affording the product as a white solid (0.24 g, 95%). M.p..163 165 o C; 1 -MR (400 Mz, CDCl 3 ): δ 0.90 p.p.m. (d, J = 5.6 z, 6), 3.57 (t, J = 7.6 z, 2), 3.88 3.86(m, 2), 4.14 (t, J = 8.4 z, 2), 7.04 (t, J = 6.8 z, 2), 7.43 (t, J = 7.2 z, 2), 7.78 (d, J = 7.2 z, 2), 8.46 (s, 2), 8.85 (t, J = 8.0 z, 2), 13.64 (s, 2). 13 C-MR (100 Mz, S6

CDCl 3 ): δ 161.77, 161.71, 151.20, 138.61, 135.47, 131.95, 128.93, 128.11, 122.93, 120.20, 114.59, 72.35, 61.70, 20.55. MALDI (m/z): [M+] + calcd for C 27 25 5 4 +, 562.109; found, 561.888. 4-omo- 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide(s I 6). To a stirred solution of (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)benzenamine (SI 4) (2.04 g, 10.0 mmol) and DMAP (0.24 g, 2.0 mmol) in C 2 Cl 2 (80 ml) and pyridine (1.5 ml) with activated 4Å molecular sieves, a solution of 4-bromopyridine-2,6-dicarbonyl dibromide (1.82 g, 4.9 mmol) in C 2 Cl 2 (10 ml) was added at 0 o C over 30 min. The mixture was stirred at room temperature for 12 h, filtered to remove molecular sieves and concentrated. Residue was purified by flash chromatography on silica gel using 92:8 (v/v) hexanes:etac affording the product as a white solid (2.85 g, 94%). M.p..182 184 o C; 1 MR (400 Mz, CDCl 3 ): δ 0.46 p.p.m. (d, J = 6.8 z, 6), 0.54 (d, J = 6.8 z, 6), 1.46 1.37 (m, 2), 3.57 3.50 (m, 2), 3.84 (t, J = 8.0, 2), 4.08 (t, J = 9.2 z, 2), 7.15 (td, J = 7.6, 1.0 z, 2), 7.54 (td, J = 7.2, 1.4 z, 2), 7.88 (dd, J = 7.8, 1.4 z, 2), 8.52 (s, 2), 8.96 (d, J = 8.4 z, 2), 13.72 (s, 2). 13 C-MR (100 Mz, CDCl 3 ): δ 162.30, 161.96, 151.48, 139.18, 135.86, 132.45, 129.23, 128.57, 123.19, 120.16, 114.67, 72.56, 69.16, 32.89, 18.17, 18.10. MALDI (m/z): [M+a] + calcd for C 31 32 5 4 a +, 640.154; found, 640.210. Me Me Bn Bn Me (S)-G1 Ether Dendrimer with Bis(benzyloxy)biphenyl Core(SI 7). A. To a solution of 2,2 -bis(benzyloxy)-3,3 -dibromobiphenyl (1.88 g, 3.6 mmol) in TF (20 ml), TMEDA (1.6 ml, 10.8 mmol) was added. The mixture was cooled to 78 o C and 1.6 M n-buli (5.6 ml, Me S7

9.0 mmol) was added dropwise. The mixture was stirred at -78 o C for 2 h, then B(Me) 3 (1.5 g, 1.6 ml, 14.4 mmol) was added dropwise at the same temperature. The mixture was warmed to 0 o C over 2 h after which time aqueous 6 a (20 ml) was added to quench excess n-buli. After stirred 2 h, the aqueous layer was separated and the organic layer was washed with 2 M a (3 10 ml). The combined aqueous extracts were acidified with conc. Cl to p 1 and extrated into ether (3x 50 ml). After drying over MgS 4, the solvent was removed in vacuo to give a light-yellow solid 2,2 -bis(benzyloxy)biphenyhl-3,3 -diyldiboronic acid (0.73 g, 45%). The crude was used directly without further purification. B. To a mixture of compound SI 3 (0.89 g, 1.42 mmol), 2,2'-bis(benzyloxy)biphenyl-3,3'- diyldiboronic acid (0.32 g, 0.71 mmol), and Pd(PPh 3 ) 4 (0.07 g, 0.057 mmol) in DME (8.5 ml), aqueous a 2 C 3 (2.8 ml, 2.8 mmol) was injected via syringe. The mixture was heated at reflux (95 o C oil bath) for 24 h. The mixture was cooled to room temperature, 2 (5 ml) and ether (10 ml) were added. The organic layer was separated and the aqueous layer was extracted into ether (3 10 ml). The combined organic extracts were washed with water (10 ml), brine (10 ml), and dried over MgS 4. After filteration and concentration, the residue was purified by flash chromatography on silica gel using 60:40 (v/v) hexanes:etac to give product (0.82 g, 70%). M.p..120 122 o C; 1 -MR (500Mz, CDCl 3 ): δ 1.13 p.p.m. (d, J = 6.4 z, 12), 3.18 (s, 12), 3.31 (dd, J = 10.6, 4.2 z, 4), 3.37 (dd, J = 10.6, 5.7 z, 4), 4.38 (s, 4), 5.02 4.97 (m, 4), 6.82 6.90 (m, 4), 7.08 7.07 (m, 6), 7.17 (td, J = 7.2, 0.9 z, 4), 7.33 (t, J = 7.6 z, 2), 7.48 (dd, J = 7.6, 1.6 z, 2), 7.63 (td, J = 7.7, 1.6 z, 6), 8.08 (dd, J = 7.9, 1.4 z, 4), 8.59 (s, 4), 8.70 (d, J = 8.1 z, 4), 12.72 (s, 4). 13 C-MR (125.70 Mz, CDCl 3 ): δ 166.66, 162.26, 154.14, 150.56, 149.30, 140.34, 136.03, 134.06, 133.74, 132.99, 132.52, 131.08, 130.36, 128.16, 127.95, 127.85, 125.61, 124.53, 123.36, 121.93, 118.45, 75.62, 74.65, 70.27, 58.93, 16.37. MALDI (m/z): [M+a] + calcd for C 84 80 6 18 a +, 1483.543; found, 1483.470. Me Me Me (S)-G1 Ether Dendrimer with Bisphenolic core (SI 8). To a solution of compound SI 7 (0.66 g, 0.4 mmol) in Et/TF (25 ml, 4/1), 10%Pd/C (0.06 g) was added. The mixture was run at 50 psi 2 for 72 h. After reaction, the catalyst was filtered with the aid of celite and concentrated. The resulting residue was purified by flash chromatography on silica gel using 92:8 (v/v) CCl 3 :acetone to give the product Me S8

(0.49 g, 96%). M.p..135 137 o C 1 -MR (400 Mz, CDCl 3 ): δ 1.13 p.p.m. (d, J = 6.2 z, 12), 3.17(s, 12), 3.36 3.29 (m, 8), 5.01 (m, 4), 6.90 (m, 2), 7.12 (t, J = 7.3 z, 4), 7.26 (t, J = 6.9 z, 2), 7.40 (d, J = 7.4 z, 2), 7.52 (t, J = 7.3 z, 4), 8.04 (d, J = 7.5 z, 4), 8.49 (d, J = 8.1 z, 4), 8.54 (s, 4), 12.65 (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ 166.65, 162.32, 151.69, 149.79, 148.95, 140.19, 133.81, 133.00, 130.97, 130.88, 125.76, 125.24, 123.30, 122.11, 121.48, 121.47, 118.75, 74.70, 70.32, 58.91, 16.40. MALDI (m/z): [M] + calcd for C 70 68 6 18, 1280.459; found, 1281.286. Me Me Bn Bn Me Me 4,4'-(2,2'-bis(benzyloxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-methyl-4,5-dihydrooxazol-2-yl)phe nyl)pyridine-2,6-dicarboxamide)(si 10). To a solution of 2,2 -bis(benzyloxy)biphenyhl-3,3 -diyldiboronic acid (0.18 g, 0.40 mmol) and 4-bromo- 2, 6 -bis(2-((s)-4-methyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide (SI 5) (0.45 g, 0.8 mmol) in DME (9 ml), Pd(PPh 3 ) 4 (0.05 g, 0.04 mmol) was added, followed by a solution of aqueous a 2 C 3 (0.17 g, 3 ml). The reaction was heated at reflux for 24 h. After cooling to room temperature, 2 (5 ml) and ether (20 ml) were added, and the organic layer was separated. The aqueous layer was back-extracted with ether (3 10 ml). The combined organic extracts were washed with water, brine, dried over MgS 4. After filtration and concentration, the residue was purified by flash chromatography on silica gel using 70:30 (v/v) hexanes:etac affording the product as a white solid (0.35 g, 66%). M.p..138 140 o C 1 -MR (400 Mz, CDCl 3 ): δ 1.02 p.p.m. (d, J = 6.8 z, 12), 3.69 (t, J = 8.0 z, 4), 4.01 3.95 (m, 4), 4.25 (t, J = 8.4 z, 4), 4.41 (s, 4), 6.79 6.77 (m, 4), 7.02 7.00 (m, 6), 7.15 (t, J = 7.6 z, 4), 7.33 (t, J = 7.6 z, 2), 7.47 (d, J =8.0 z, 2), 7.66 7.54 (m, 4), 7.67 (d, J =6.4, 2), 7.88 (d, J = 7.2 z, 4), 8.52 (s, 4), 8.97 (d, J = 8.4 z, 4), 13.65 (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ 163.55, 162.12, 154.04, 150.28, 149.83, 139.33, 135.97, 133.63, 132.91, 132.35, 130.23, 129.25, 128.16, 128.06, 127.82, 125.80, 124.50, 122.96, 120.60, 114.95, 75.75, 72.78, 62.11, 20.95. MALDI (m/z): [M+a] + calcd for C 80 68 10 10 a +, 1351.502; found, 1351.766. S9

Me Me Me Me 4,4'-(2,2'-dihydroxybiphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-methyl-4,5-dihydrooxazol-2-yl)phenyl) pyridine-2,6-dicarboxamide) (SI 12). To a solution of 4,4'-(2,2'-bis(benzyloxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-methyl-4,5-dihydrooxazol-2-yl)-phenyl)pyridine-2,6-dicarboxamide)(si 10) (0.35 g, 0.26 mmol) in Et/TF (30 ml, 3/1) was added 10% Pd/C (0.04 g). The reaction was run at 50 psi 2 for 48 h. After reaction, the mixture was filtered through celite to remove Pd/C and concentrated. The residue was purified by flash chromatography on silica gel using 8:17:75 (v/v) Me:C 2 Cl 2 : hexanes affording the product as a white solid (0.19 g, 64%). M.p..182 184 o C 1 -MR (500 Mz, CDCl 3 ): δ 1.10 p.p.m. (d, J = 6.5 z, 12), 3.72 (t, J = 8.0 z, 4), 4.05 (m, 4), 4.26 (t, J = 8.0 z, 4), 6. 60 (s, 2), 7.18 7.11 (m, 10), 7.49 (t, J = 7.5 z, 4,), 7.90 (t, J = 7.0 z, 4), 8.35 (s, 4), 8.86 (d, J = 8.5 z, 4), 13.52 (s, 4). 13 C-dept135 MR (125.7 Mz, CDCl 3 ): δ 133.16, 132.08, 130.98, 129.16, 124.95, 122.83, 121.37, 121.10, 72.90, 62.28, 30.91, 21.18. MALDI (m/z): [M+a] + calcd for C 66 56 10 10 a + 1171.408; found, 1171.463. Bn Bn 4,4'-(2,2'-bis(benzyloxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)- phenyl)pyridine-2,6-dicarboxamide)(si 11). To a solution of 2,2 -bis(benzyloxy)biphenyhl-3,3 -diyldiboronic acid (0.44 g, 0.96 mmol), and 4-bromo- 2, 6 - bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide (SI 6) (1.14 g, 1.85 mmol) in DME (24.0 ml) was added Pd(PPh 3 ) 4 (0.10 g, 0.09 mmol), followed by a solution of aqueous S10

a 2 C 3 (8 ml, 4 mmol). The mixture was heated at reflux for 24 h. Water (10 ml) and ether (20 ml) were added and the organic layer was separated. The aqueous layer was back-extracted with ether (3 10 ml), and the combined organic extracts were washed with water, brine, dried over MgS 4. After filteration and concentration, the residue was purified by flash chromatography on silica gel using 70:30 (v/v) hexanes:etac affording the product as a white solid (0.8 mg, 58%). M.p..170 172 o C 1 -MR(400 Mz, CDCl 3 ): δ 0.51 p.p.m. (d, J = 6.5 z, 12), 0.61 (d, J = 6.5 z, 12), 1.50 1.42 (m, 4), 3.63 3.57 (m, 4), 3.86 (t, J = 8.2 z, 4), 4.12 (t, J = 8.5 z, 4), 4.40 (s, 4), 6.77 6.75 (m, 4), 7.04 7.02 (m, 6), 7.15 (td, J = 7.3, 1.0 z, 4), 7.34 (t, J = 7.8 z, 2), 7.50 (dd, J = 7.6, 1.7 z, 2), 7.56 (td, J = 7.2, 1.6 z, 4), 7.69 (dd, J = 7.6, 1.6 z, 2), 7.90 (dd, J = 7.8, 1.5 z, 4), 8.52 (s, 4), 9.08 (dd, J = 8.3, 0.6 z, 4), 13.69 (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ 163.69, 161.97, 153.90, 150.38, 149.76, 139.65, 135.84, 133.66, 132.96, 132.82, 132.44, 130.24, 129.22, 128.31, 128.10, 127.90, 125.87, 124.47, 122.81, 120.18, 114.65, 75.64, 72.70, 69.19, 32.98, 18.30, 18.17. MALDI (m/z): [M+a] + calcd for C 88 84 10 10 a +, 1463.627; found, 1463.811. 4,4'-(2,2'-dihydroxybiphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)phen yl)pyridine-2,6-dicarboxamide) (SI 13). To a solution of 4,4'-(2,2'-bis(benzyloxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)-phenyl)pyridine-2,6-dicarboxamide) (SI 11) (0.8 g, 0.56 mmol) in Et/TF (20 ml, 3/1), was added 10% Pd/C (0.08 g). The reaction was run at 50 psi 2 for 48 h. After reaction, the mixture was filtered through celite to remove Pd/C and concentrated. The residue was purified by flash chromatography on silica gel using 5:15:80 (v/v) Me:TF: hexanes affording the product as white solid (0. 46 g, 65%). M.p. 210 212 o C 1 -MR (400 Mz, CDCl 3 ): δ 0.50 p.p.m. (d, J = 6.7 z, 12), 0.56 (d, J = 6.7 z, 12), 1.60 1.51 (m, 4), 3.66 3.60 (m, 4), 3.86 (t, J = 8.2 z, 4), 4.08 (t, J = 8.4 z, 4), 6.80 (s, 2), 7.10 (t, J = 7.6 z, 4), 7.23 (d, J = 6.0 z, 2), 7.33 (d, J = 7.4 z, 2), 7.48 (td, J = 8.4, 1.0 z, 4), 7.86 (dd, J = 7.8, 1.0 z, 4), 8.51 (s, 4), 8.90 (d, J = 8.3 z, 4), 13.56 (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ 163.46, 161.87, 151.56, 150.10, 148.73, 139.52, 132.93, 132.21, 130.94, 129.11, 125.50, 125.24, 125.22, 124.62, 122.74, 121.45, 114.75, 72.57, 68.82, 32.60, 18.43, 17.75. MALDI (m/z): [M+a] + calcd for C 74 72 10 10 a +, 1283.533; found, 1283.628 S11

Bn Bn 4,4'-((R)-2,2'-bis(benzyloxy)-1,1'-binaphthyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydro oxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide)( SI (R)-16). A. To a solution of (R)-2,2'-bis(benzyloxy)-3,3'-dibromo-1,1'-binaphthyl (0.63 g, 1.0 mmol) in TF (5 ml), TMEDA (0.45 ml, 3.0 mmol) was added. The mixture was cooled to 78 o C, and1.6 M n-buli (1.56 ml, 2.5 mmol) was added dropwise. After stirring at -78 o C for 2 h, B(Me) 3 (0.42 g, 0.45 ml, 4.0 mmol) was added dropwise. The mixture was warmed to 0 o C over 2 h. Aqueous 6 a (5 ml) was added to quench excess n-buli. After 2 h, the aqueous was separated and the organic layer was washed with 2 M a (3 10 ml). The combined aqueous extracts were acidified with conc. Cl to p 1. The aqueous layer was extracted with ether (3 x 30 ml). The ether layer was dried over MgS 4, filtered and concentrated to give a light-yellow solid (R)-2,2'-bis(benzyloxy)-1,1'-binaphthyl-3,3'- diyldiboronic acid (0.288 g, 52%), the crude was used directly with further purification. B. To a solution of (R)-2,2'-bis(benzyloxy)-1,1'-binaphthyl-3,3'-diyldiboronic acid (0.22 g, 0.4 mmol), 4-bromo- 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide (SI 6) (0.49 g, 0.8 mmol) in DME (10 ml), was added Pd(PPh 3 ) 4 (0.05 g, 0.04 mmol) followed by a solution of aqueous a 2 C 3 (3.2 ml, 1.6 mmol). The reaction was heated at reflux for 24 h. Water (2 ml) and ether (10 ml) were added. The organic layer was separated and the aqueous layer was extracted with ether (3 10 ml). The combined organic extracts were washed by water, brine and dried over MgS 4. After filtration and concentration, the residue was purified by flash chromatography on silica gel using 70:20:10 (v/v) hexanes:c 2 Cl 2 :acetone. The product was isolated as a white solid (0.28 g, 45%). M.p.210 212 o C 1 -MR (250 Mz, CDCl 3 ): δ 0.53 p.p.m. (d, J = 6.6 z, 12), 0.64 (d, J = 6.6 z, 12), 1.54 1.41 (m, 4), 3.62 (q, J = 8.3 z, 4), 3.87 (t, J = 8.4 z, 4), 4.12 (t, J = 8.8 z, 4), 4.39 (d, J = 11.0 z, 2), 4.54 (d, J = 11.0 z, 2), 6.56 6.53 (m, 4), 6.95-6.92 (m, 6), 7.15 (t, J = 7.5 z, 4), 7.42 (d, J = 5.7 z, 4), 7.60 7.50 (m, 6), 7.92 (d, J = 7.8 z, 4), 8.01 (d, J = 8.0 z, 2), 8.16 (s, 4), 8.63 (s, 4), 9.08 (d, J = 8.4 z, 4), 13.74 (s, 4). 13 C-MR (62.9 Mz, CDCl 3 ): 163.56, 161.90, 152.36, 150.32, 149.68, 139.62, 139.54, 135.92, 134.52, 132.37, 131.00, 130.69, 129.15, 128.57, 128.52, 127.82, 127.73, 127.58, 127.47, 126.53, 125.88, 125.71, 122.74, 120.05, 114.50, 75.41, 72.57, 69.13, 32.91, 18.20, 18.13. MALDI (m/z): [M+a] + calcd for C 96 88 10 10 a +, 1563.658; found, 1563.819. S12

4,4'-((R)-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol -2- yl)phenyl)pyridine-2,6-dicarboxamide) ( SI (R)-17). To a solution of 4,4'-((R)-(2,2'-bis(benzyloxy)-1,1'-binaphthyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl- 4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide) (SI (R)-16) (0.2 g, 0.13 mmol) in Et/TF (12 ml, 3/1), was added 10% Pd() 2 /C (0.02 g). The reaction was run at 50 psi 2 for 48 h. After reaction was complete, the mixture was filtered through celite to remove Pd/C and concentrated. The residue was purified by flash chromatography on silica gel using 79:20:1 (v/v) hexanes:tf:me affording the product as a white solid (0.074 g, 42%). M.p.238 240 o C. 1 -MR (400 Mz, CDCl 3, 45 o C): δ 0.52 p.p.m. (d, J = 6.4 z, 12), 0.66 (d, J = 5.6 z, 12), 1.57 (m, 4), 3.55 (m, 4), 3.87 (t, J = 8.1 z, 4), 4.05 (t, J = 8.8 z, 4), 6.96 (m, 2), 7.01 (t, J = 6.8 z, 4), 7.17 (m, 2), 7.28 (d, J = 8.3 z, 2), 7.45 (t, J = 7.2 z, 4), 7.78 (d, J = 7.0 z, 6), 8.21 (s, 2), 8.43 (s, 4), 8.93 (d, J = 7.2 z, 4), 13.53 (s, 4). 13 C-MR (100 Mz, CDCl 3 ): 163.04, 162.05, 150.22, 150.12, 148.89, 139.62, 134.32, 132.33, 132.27, 132.04, 129.06, 128.88, 128.56, 128.08, 126.91, 125.36, 124.00, 123.88, 122.65, 120.61, 114.74, 72.62, 68.81, 32.52, 18.60, 17.75. MALDI (m/z): [M+a] + calcd for C 82 76 10 10 a +, 1383.564; found, 1383.939. PPh 2 PPh 2 Ph Ph P P Rh SbF 6 Ph Ph (S)-2,2'-Bis(diphenylphosphinooxy)-1,1'-binaphthyl [6] and [BIP]Rh + Catalyst C1 [7] A. In drybox, to a solution of (S)-BIL (131.7 mg, 0.46 mmol) and DMAP (118 mg, 2.1 e.q.) in TF (2 ml), Ph 2 PCl (0.0164 ml, 2.1 eq.) was added, which resulted in the immediate formation of a white precipitation. The mixture was allowed to stir for 4 h. The white solid was removed by filtration filteration through a small pad of celite. After evaporation of the solvent, the residue was purified by recrystallization with C 2 Cl 2 /hexanes to give 0.23 g product, yield 76%. 31 P MR (101.3 Mz, CDCl 3 ): δ 110.57. B. In a drybox, (S)-2,2'-bis(diphenylphosphinooxy)-1,1'-binaphthyl (20 mg, 0.031 mmol) in 0.2 ml of C 2 Cl 2 was added slowly to a solution of Rh + (CD) 2 SbF 6 - (17.0 mg, 0.031 mmol) in C 2 Cl 2 (0.2 ml) at S13

room temperature. After 2 h, the mixture was concentrated to give the product [BIP]Rh + (C1) as an orange solid. 31 P MR (101.3 Mz, CDCl 3 ): δ 128.02 (d, J P-Rh = 169.45 z). Me Me Me Me PPh 2 PPh 2 Ph 2 P Rh P Ph 2 SbF 6 Me Me Phosphine Dendrimer(SI 9) and [Dend]Rh + Catalyst(C2) A. In a drybox, to a solution of SI 8 (100 mg, 0.078 mmol) and DMAP (20 mg, 2.1 e.q.) in TF (1 ml), Ph 2 PCl (0.029 ml, 0.164 mmol, 2.1 e.q.) was added dropwise resulting in the immediate formation of a white precipitation. After stirring for 4 h, the white solid was removed by filteration through a pad of celite. After evaporation of the solvent, residue was purified with recrystallizaion in C 2 Cl 2 /hexanes to give product (90 mg, 70%). 31 P MR (161.9 Mz, CDCl 3 ): δ 121.15, 121.10. B. Compound SI 9 (26.5 mg, 0.016 mmol) in C 2 Cl 2 (0.2 ml) was added slowly to a solution of Rh + (CD) 2 SbF 6 - (8.9 mg, 0.016 mmol) in C 2 Cl 2 (0.2 ml). After 2 h, the mixture was concentrated to give orange solid, [Dend]Rh + (C2). 31 P MR (161.9 Mz, CDCl 3 ): δ 140.90 (d, J P-Rh = 179.8 z). Me Me PPh 2 PPh 2 Me Me MeMe Me Me Ph 2 P P Ph 2 Rh SbF 6 MeMe 4,4'-(2,2'-bis(diphenylphosphinooxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-methyl-4,5-dihydroox azol-2-yl)phenyl)pyridine-2,6-dicarboxamide)(si 14) and [Dend]Rh + Catalyst(C3) A. In a drybox, to a stirred solution of 4,4'-(2,2'-dihydroxybiphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-methyl-4,5-dihydro-oxazol-2-yl)phenyl)pyri S14

dine-2,6-dicarboxamide) (SI 12) (75.8 mg, 0.066 mmol) and DMAP (16.9 mg, 2.1 e.q.) in TF (0.4 ml) was added Ph 2 PCl (0.0248 ml, 0.138 mmol, 2.1 e.q.). A white precipitation was formed immediately. After stirring for 4 h, the solid was removed by filteration through a pad of Celite. After evaporation of the solvent, the residue was purified by recrystallizaion with C 2 Cl 2 /hexanes to give product (70 mg, 61%). 31 P MR(101.3 Mz, CDCl 3 ): δ 120.71, 120.30.. B. To a solution of Rh + (CD) 2 SbF 6 - (10.5 mg, 0.019 mmol) in C 2 Cl 2 (0.2 ml), compound SI 14 (28.8 mg, 0.019 mmol) in C 2 Cl 2 (0.2 ml) was added slowly. After 2 h, the mixture was concentrated to give orange solid, [Dend]Rh + Catalyst(C3). 31 P MR (101.3Mz, CDCl 3 ): δ 133.28 (d, J P-Rh = 171.4 z), 133.06 (d, J P-Rh = 171.4 z). PPh 2 PPh 2 Ph 2 P P Ph 2 Rh SbF 6 4,4'-(2,2'-bis(diphenylphosphinooxy)biphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydro oxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide)(si 15) and [Dend]Rh + catalyst (C4) A. In a drybox, to a stirred solution of 4,4'-(2,2'-dihydroxybiphenyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4 -iso-propyl-4,5-dihydro-oxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide) (SI 13) (44.1 mg, 0.035 mmol) and DMAP (8.9 mg, 2.1 e.q.) in TF (0.4 ml) was added Ph 2 PCl (0.0132 ml, 0.073 mmol, 2.1 e.q.). A white precipitation was formed immediately. After 4 h, the solid was removed by filteration through a pad of celite. After evaporation of the solvent, the residue was purified by recrystallizaion with C 2 Cl 2 / hexanes to give product (46.3 mg, 81%). 31 P MR (101.3Mz, CDCl 3 ): δ 120.37, 119.97. B. To a solution of Rh + (CD) 2 SbF 6 - (15.7 mg, 0.028 mmol) in C 2 Cl 2 (0.2 ml), compound SI 15 (46.3 mg, 0.028 mmol) in C 2 Cl 2 (0.2 ml) was added slowly. After stirred 2 h, the mixture was concentrated to give orange solid, [Dend]Rh + catalyst (C4). 31 P MR (101.3 Mz, CDCl 3 ): δ 133.21 (d, J P-Rh = 172.8 z), 132.91 (d, J P-Rh = 171.6 z).. S15

PPh 2 PPh 2 Ph 2 P P Ph 2 Rh SbF 6 4,4'-((R)-2,2'-bis(diphenylphosphinooxy)-1,1'-binaphthyl-3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5- dihydrooxazol- 2-yl)phenyl)pyridine-2,6-dicarboxamide)( SI (R)-18) and [Dend]Rh + Catalyst (C5) A. In a drybox, to a stirred solution of 4,4'-((R)-2,2'-dihydroxy-1,1'-binaphthyl- 3,3'-diyl)bis( 2, 6 -bis(2-((s)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)pyridine-2,6-dicarboxamide) (SI (R)-17) (90.3 mg, 0.066 mmol) in dry TF (0.5 ml) and DMAP (16.6 mg, 2.05 eq.), Ph 2 PCl (0.024 ml, 0.136 mmol, 2.05 eq.) was added dropwise. A white precipitation formed immediately. After 4 h, solid was removed by filteration through a pad of celite. After evaporation of the solvent, the residue was purified by recrystallizaion with C 2 Cl 2 /hexanes to give product (74 mg, 65%). 31 P MR(101.3 Mz, CDCl 3 ): δ 117.44. B. To a stirred solution of Rh + (CD) 2 SbF 6 - (5.6 mg, 0.010 mmol) in C 2 Cl 2 (0.2 ml), compound SI (R)-18 (17.5 mg, 0.010 mmol) in C 2 Cl 2 (0.2 ml) was added slowly. After 2 h the mixture was concentrated to give a orange solid, [Dend]Rh + Catalyst (C5). 31 P MR (101.3 Mz, CDCl 3 ): δ 134.40 (d, J P-Rh = 169.9 z). ydrogenation Reaction (Z)-methyl 2-acetamido-3-phenylacrylate (0.15 mmol) was dissolved in solvent (2 ml) and placed in a Fischer-Porter apparatus in a drybox. The Rh catalyst (0.0005 mmol) in the solvent (2 ml) was added to the substrate solution. The Fischer-Porter tube was removed from the drybox, and the reaction was placed under 50 psi hydrogen after three evacuation-refill cycles. After reaction, the solvent was removed, residue was dissolved in C 2 Cl 2 and purified by flash chromatography on silica gel using 50:50(v/v) hexanes:etac. The residue was analyzed by GC with chirality capillary column (Chirasil-L-VAL, 25 m 0.25 mm, injector temperature 250 o C, detector temperature 250 o C, column temperature 170 o C). Retention time: (R)-isomer 12.8 min, (S)-isomer 14.0 min, starting material 32.3 min. The reaction was exceptionally clean and the yield nearly quantitative. Each reaction was repeated twice, and the ee s are recorded. Absolute configurations of the product enantiomers were determined by comparison of GC retention times in reference [7]. S16

References 1. Alexakis, Alexandre; Polet, Damien; Rosset, Stephane; March, Sebastien. J. rg. Chem. 2004, 69, 5660 5667. 2. Xu, Yingjian; Clarkson, Guy C.; Docherty, Gordon; orth, Carl L.; Woodward, Gary; Wills, Martin. J. rg. Chem. 2005, 70, 8079 8087 3 Gabriel, Christopher J.; DeMatteo, Matthew P.; Paul, oel M.; Takaya, Tomohisa; Gustafson, Terry L.; adad, Christopher M.; Parquette, Jon R. J. rg. Chem. 2006, 71, 9035 9044 4. Kurosu, Michio; Lin Mei-uey; Kishi Yoshito, J. Am. Chem. Soc. 2004, 126, 12248 12249 5. Preston, Adam J.; Fraenkel, Gideon; Chow, Albert; Gallucci, Judith C.; Parquette, Jon R.. J. rg. Chem. 2003, 68, 22 26 6. Clyne, D. S., Mermet-Bouvier, Y. C., omura,. & RajanBabu, T. V. J. rg. Chem. 64, 7601-7611 (1999). 7. Zhang, F.Y.; Kwok W..; Chan Albert S.C., Tetrahedron: Asymmetry 2001, 12, 2337 2342 8. RajanBabu T.V.; Ayers T.A.; alliday G.A.; You K.K.; Calabrese J.C. J. rg. Chem. 1997, 62, 6012 6028 S17

Copies of 1 -, 13 C- and 31 P-MR Spectra for Synthetic Intermediates and C1-C5 S18

Bn Bn 1.999 2.067 5.995 4.037 2.199 4.094 7.7591 7.7551 7.7391 7.7351 7.4508 7.4469 7.4317 7.4278 7.3861 7.3813 7.3762 7.3697 7.2634 7.2543 7.2452 7.2396 7.1631 7.1435 7.1240 4.8455 PPM 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 file: F:\MR for paper 1\Done\yjf104-1\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 21 freq. of 0 ppm: 400.129991 Mz LB: 0.300 GB: 0.0000 S19

136.3788 133.5170 133.2091 130.8376 128.1591 128.1418 127.9046 124.9877 118.0006 77.3157 76.9972 76.6799 74.7770 Bn Bn PPM 132.0 128.0 124.0 120.0 116.0 112.0 108.0 104.0 100.0 96.0 92.0 88.0 84.0 80.0 76.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf104-1\3\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 178 freq. of 0 ppm: 100.612793 Mz LB: 1.000 GB: 0.0000 S20

1.999 2.009 2.139 2.044 2.074 5.971 3.988 2.011 2.016 8.3943 7.9263 7.9059 7.5343 7.5162 7.4973 7.3965 7.3762 7.3590 7.3109 7.2902 7.2379 6.9624 6.9519 6.9446 5.0948 5.0686 4.7086 4.6824 Bn Bn PPM 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 file: Z:\jyu\MR total\2007\yjf283\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 10 freq. of 0 ppm: 400.129992 Mz LB: 0.300 GB: 0.0000 S21

151.6489 136.5849 133.0694 132.8880 131.4863 127.9454 127.6541 127.6012 127.1157 127.0846 126.8929 125.9011 117.7325 77.3131 76.9951 76.6775 75.0303 Bn Bn PPM 148.0 144.0 140.0 136.0 132.0 128.0 124.0 120.0 116.0 112.0 108.0 104.0 100.0 96.0 92.0 88.0 84.0 80.0 76.0 72.0 file: Z:\jyu\MR total\2007\yjf283\2\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 89 freq. of 0 ppm: 100.612785 Mz LB: 1.000 GB: 0.0000 S22

Me Me 1.998 2.105 2.074 2.104 2.094 2.123 2.116 1.993 2.247 6.365 6.238 12.6794 8.6285 8.6270 8.6080 8.6062 8.5613 8.0749 8.0713 8.0551 8.0513 7.6312 7.6275 7.6097 7.5921 7.5884 7.2396 7.2000 7.1619 7.1593 7.1975 7.1798 4.9791 4.9524 4.9681 4.9643 4.9487 4.9377 3.3754 3.3611 3.3562 3.3488 3.3345 3.3163 3.3057 3.2963 3.2897 3.2791 3.1818 3.1693 1.1204 1.1042 PPM 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Done\yjf92\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 17 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S23

166.6075 160.9735 150.3209 139.8402 136.5315 134.1081 131.0859 128.3957 123.7420 121.9022 118.4640 77.3099 76.9924 76.6752 74.5836 70.3529 58.9292 16.3135 Me Me PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: F:\MR for paper 1\yjf92\2\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 290 freq. of 0 ppm: 100.612773 Mz LB: 1.000 GB: 0.0000 S24

1.000 1.007 1.016 1.045 1.960 1.046 1.040 1.067 1.040 3.139 3.140 7.6773 7.6742 7.6615 7.6583 7.2397 7.1955 7.1924 7.1810 7.1787 7.1762 7.1648 7.1616 6.6864 6.6703 6.6520 6.6498 6.6374 6.6359 6.6218 6.6196 6.1243 4.3204 4.3038 4.3019 4.2853 4.1046 4.0908 4.0877 4.0858 4.0721 4.0077 3.9916 3.9756 1.7949 1.7814 1.7680 1.7546 1.0215 1.0081 0.9321 0.9187 2 PPM 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf11B\1\fid expt: <zg30> transmitter freq.: 500.023088 Mz width: 10330.58 z = 20.660203 ppm = 0.157632 z/pt number of scans: 22 freq. of 0 ppm: 500.020022 Mz LB: 0.300 GB: 0.0000 S25

163.5055 148.5817 131.8600 129.5432 115.9310 115.5850 109.1443 77.2468 76.9933 76.7392 72.8581 68.7081 33.1548 18.9224 18.5552 2 PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf11B\2\fid expt: <zgpg30> transmitter freq.: 125.742702 Mz width: 30030.03 z = 238.821256 ppm = 0.458222 z/pt number of scans: 105 freq. of 0 ppm: 125.730135 Mz LB: 1.000 GB: 0.0000 S26

2.000 2.014 1.992 2.037 2.011 2.032 1.972 2.045 1.987 6.088 8.8592 8.8392 8.4563 7.7904 7.7724 7.4465 7.4289 7.4107 7.0555 7.0211 4.1634 4.1428 4.1222 3.8845 3.8671 3.5922 3.5729 3.5538 0.9124 0.8981 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: G:\yjf13C\proton\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 26 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S27

161.7733 161.7096 151.1981 138.6038 135.4706 131.9491 128.9307 128.1090 122.9250 120.1995 114.5886 77.3131 76.9934 76.6746 72.3461 61.7002 20.5484 PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: G:\yjf13C\carbon\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 72 freq. of 0 ppm: 100.612802 Mz LB: 1.000 GB: 0.0000 S28

162.2993 161.9565 151.4843 139.1768 135.8638 132.4532 129.2300 128.5712 123.1875 120.1605 114.6682 77.3118 76.9947 76.6765 72.5633 69.1602 32.8868 18.1724 18.0964 PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: F:\MR for paper 1\BW-III-51\1\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 138 freq. of 0 ppm: 100.612774 Mz LB: 0.300 GB: 0.0000 S29

1.997 2.086 1.838 2.113 2.100 2.075 2.059 2.103 2.101 2.160 6.297 6.208 13.7207 8.9717 8.9506 8.5229 7.8873 7.8837 7.8677 7.8641 7.5650 7.5614 7.5436 7.5257 7.5219 7.2397 7.1657 7.1463 7.1277 7.1252 7.1632 4.0812 4.0783 4.0571 4.1024 3.8612 3.8406 3.8200 3.5668 3.5487 3.5469 3.5428 3.5288 3.5250 3.5049 1.4558 1.4391 1.4223 1.4055 1.3888 1.3721 0.5535 0.5367 0.4718 0.4551 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Done\yjf12B\2\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 16 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S30

4.002 3.618 4.030 3.725 5.959 1.979 1.937 4.319 6.197 4.184 4.019 4.002 4.225 4.173 12.31 12.56 12.7234 8.7091 8.6929 8.5892 8.0898 8.0871 8.0740 8.0711 7.6534 7.6502 7.6380 7.6230 7.6088 7.6060 7.4898 7.4866 7.4745 7.4714 7.3474 7.3321 7.3168 7.2401 7.1739 7.1899 7.1882 7.1596 7.1578 7.0669 7.0800 7.0775 7.0712 6.8042 6.8187 6.8115 6.8004 5.0250 5.0125 5.0033 5.0007 4.9911 4.9793 4.9667 4.3792 3.3890 3.3775 3.3677 3.3563 3.3296 3.3211 3.3084 3.2998 3.1859 1.1423 1.1294 Me Me x 1.000 Bn Bn 3.618 4.030 3.725 5.959 1.979 1.937 4.319 6.197 4.184 8.4 8.0 7.6 7.2 6.8 Me Me PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Done\yjf156-1\1\fid expt: <zg30> transmitter freq.: 500.023088 Mz width: 10330.58 z = 20.660203 ppm = 0.157632 z/pt number of scans: 20 freq. of 0 ppm: 500.020021 Mz LB: 0.300 GB: 0.0000 S31

166.6535 162.2604 154.1316 150.5597 149.3040 140.3368 136.0309 134.0537 133.7357 132.9882 132.5184 131.0748 130.3608 128.1555 127.9465 127.8517 125.6119 124.5285 123.3621 121.9237 118.4474 77.2508 76.9964 76.7421 75.6237 74.6464 70.2685 58.9342 16.3716 Me Me Bn Bn Me Me PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: F:\MR for paper 1\Done\yjf156-1\3\fid expt: <zgpg30> transmitter freq.: 125.742702 Mz width: 30030.03 z = 238.821256 ppm = 0.458222 z/pt number of scans: 1696 freq. of 0 ppm: 125.730131 Mz LB: 1.000 GB: 0.0000 S32

3.785 7.869 3.969 3.920 1.998 2.172 4.171 2.176 3.998 8.266 12.32 12.10 12.6514 8.5370 8.5055 8.4852 8.0516 8.0328 7.5359 7.5177 7.4993 7.4165 7.3988 7.2760 7.2587 7.2393 7.1425 7.1242 7.1060 6.9047 5.0113 4.9992 3.3869 3.3608 3.3474 3.3296 3.3199 3.3047 3.2940 3.1741 1.1392 1.1237 Me Me Me Me PPM 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf157 pure again\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 27 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S33

166.6464 162.3191 151.6906 149.7917 148.9530 140.1909 133.8101 132.9973 130.9667 130.8786 125.7600 125.2362 123.2972 122.1118 121.4846 121.4672 118.7481 Me Me 77.3296 77.0116 76.6944 74.6992 70.3176 58.9123 16.3948 Me Me PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: F:\MR for paper 1\Done\yjf157 pure again\3\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 831 freq. of 0 ppm: 100.612767 Mz LB: 1.000 GB: 0.0000 S34

Bn Bn 3.985 3.998 3.956 4.236 2.911 4.478 2.628 1.984 4.346 6.067 3.940 3.615 4.048 4.267 4.109 11.98 13.6545 8.9851 8.9644 8.5165 7.8963 7.8932 7.8767 7.8736 7.6802 7.6774 7.6619 7.6590 7.5788 7.5752 7.5573 7.4772 7.4813 7.4621 7.4584 7.3306 7.3497 7.3115 7.2399 7.1564 7.1759 7.1742 7.1380 7.1359 7.0157 7.0107 7.0203 7.0044 6.7878 6.7789 6.7699 6.7644 4.4103 4.2699 4.2487 4.2266 4.0061 3.9851 3.9682 3.9506 3.9461 3.7072 3.6868 3.6663 1.0335 1.0170 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Done\yjf276-1 new\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 128 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S35

163.5542 162.1186 154.0356 150.2786 149.8320 139.3261 135.9659 133.6299 132.9102 132.8912 132.3513 130.2272 129.2517 128.1593 128.0816 127.8131 125.7961 124.4941 122.9593 120.5999 114.9467 77.3141 76.9962 76.6789 75.7460 72.7789 62.1004 20.9397 Bn Bn PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: C:\Documents and Settings\jianfengyu yu\desktop\yjf276-1c\1\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 11932 freq. of 0 ppm: 100.612770 Mz LB: 1.000 GB: 0.0000 S36

3.998 3.979 3.925 4.261 4.240 9.206 1.975 4.240 4.279 4.375 12.83 13.5180 8.8664 8.8500 8.3515 7.9081 7.9064 7.8928 7.8908 7.5098 7.4947 7.4794 7.2398 7.1833 7.1692 7.1568 7.1416 7.1261 7.1075 6.5960 4.2799 4.2620 4.2454 4.0638 4.0479 4.0337 4.0168 3.7337 3.7176 3.7016 1.1030 1.0899 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: C:\Documents and Settings\jianfengyu yu\desktop\check yjf276\1\fid expt: <zg30> transmitter freq.: 500.023088 Mz width: 10330.58 z = 20.660203 ppm = 0.157632 z/pt number of scans: 18 freq. of 0 ppm: 500.020022 Mz LB: 0.300 GB: 0.0000 S37

133.1657 132.0853 130.9815 129.1592 124.9504 122.8307 121.3668 121.0956 72.9052 62.2761 30.9105 21.1757 PPM 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: Z:\jyu\MR total\check yjf276\2\fid expt: <dept135> transmitter freq.: 125.742702 Mz width: 30030.03 z = 238.821256 ppm = 0.458222 z/pt number of scans: 57 freq. of 0 ppm: 125.730129 Mz LB: 1.000 GB: 0.0000 S38

Bn Bn 4.000 3.972 3.919 3.994 1.936 4.097 2.046 2.042 4.173 5.987 4.060 4.082 4.067 4.195 4.156 4.199 13.6871 9.0610 9.0596 9.0403 9.0386 8.5203 7.9127 7.9089 7.8930 7.8892 7.7018 7.6976 7.6827 7.6785 7.5848 7.5415 7.5119 7.5809 7.5077 7.5631 7.5454 7.4928 7.4886 7.3598 7.3407 7.3217 7.2398 7.1665 7.1690 7.1491 7.1482 7.1311 7.1284 7.0222 7.0391 7.0339 7.0262 6.7706 6.7657 6.7572 6.7469 4.3999 4.1339 4.1128 4.1096 4.0887 3.8832 3.8625 3.8419 3.6140 3.6105 3.5958 3.5924 2.1489 1.5633 1.4717 1.4548 12.21 12.13 0.6183 0.6016 0.5176 0.5009 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274-1\1\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 128 freq. of 0 ppm: 400.130018 Mz LB: 0.300 GB: 0.0000 S39

163.6938 161.9651 153.8973 150.3754 149.7628 139.6539 135.8443 133.6583 132.9622 132.8183 132.4411 130.2361 129.2171 128.3057 128.1033 127.8980 125.8717 124.4730 122.8142 120.1772 114.6532 77.3142 76.9963 76.6788 75.6412 72.7033 69.1909 32.9858 18.3025 18.1737 Bn Bn PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274-1\2\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 11950 freq. of 0 ppm: 100.612771 Mz LB: 1.000 GB: 0.0000 S40

3.998 4.032 4.000 4.190 4.188 2.081 2.663 4.258 2.069 4.166 4.101 3.991 4.259 12.30 11.94 13.5582 8.9120 8.8912 8.5119 7.8722 7.8685 7.8525 7.8489 7.5045 7.5009 7.4830 7.4651 7.4614 7.3456 7.3271 7.2403 7.2249 7.0989 7.1184 7.1161 7.0805 7.0781 6.8020 4.0988 4.0900 4.0777 4.0746 4.0538 3.8823 3.8618 3.8413 3.6614 3.6415 3.6213 3.6007 1.5956 1.5795 1.5632 1.5467 1.5302 1.5137 0.5663 0.5495 0.4991 0.4824 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274C\2\fid expt: <zg30> transmitter freq.: 400.132471 Mz width: 8278.15 z = 20.688513 ppm = 0.126314 z/pt number of scans: 66 freq. of 0 ppm: 400.130024 Mz LB: 0.300 GB: 0.0000 S41

163.4587 161.8691 151.5577 150.1038 148.7256 139.5237 132.9315 132.2095 130.9458 129.1130 125.5006 125.2438 125.2169 124.6186 122.7414 121.4510 114.7544 77.3132 76.9953 76.6773 72.5747 68.8163 32.5983 18.4274 17.7486 PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274C\1\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 344 freq. of 0 ppm: 100.612773 Mz LB: 1.000 GB: 0.0000 S42

3.825 13.7353 3.917 3.906 1.934 2.067 4.163 6.085 4.100 4.037 6.079 3.911 1.999 2.098 4.176 4.076 4.085 4.304 12.02 11.66 9.1004 9.0668 8.6296 8.1547 8.0265 7.9945 7.9025 7.6026 7.5726 7.5386 7.5174 7.4996 7.4851 7.4104 7.4246 7.1801 7.1500 7.1194 6.9471 6.9230 6.5591 6.5290 6.5369 4.5618 4.5181 4.4121 4.3684 4.1608 4.1243 4.0887 3.8994 3.8665 3.8337 3.6678 3.6361 1.5397 1.5153 1.4890 1.4624 1.4358 1.4096 0.6511 0.6248 0.5399 0.5137 (R) Bn Bn (S) (S) (S) (S) PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Syjf286 pure\1\fid expt: <zg30> transmitter freq.: 250.131545 Mz width: 5175.98 z = 20.693046 ppm = 0.078979 z/pt number of scans: 16 freq. of 0 ppm: 250.130011 Mz LB: 0.300 GB: 0.0000 S43

163.5553 161.8967 152.3601 150.3240 149.6773 139.6161 139.5403 135.9252 134.5156 132.3662 130.9977 130.6890 129.1468 128.5699 128.5191 127.8196 127.7270 127.5789 127.4698 126.5320 125.8787 125.7144 122.7434 120.0520 114.5025 77.5064 76.9973 76.4885 75.4098 72.5720 69.1328 32.9087 18.2022 18.1313 Bn Bn PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 file: F:\MR for paper 1\Done\Syjf286 pure\3\fid expt: <zgpg30> transmitter freq.: 62.901528 Mz time domain size: 32768 points width: 15060.24 z = 239.425677 ppm = 0.459602 z/pt number of scans: 183 freq. of 0 ppm: 62.895248 Mz LB: 1.000 GB: 0.0000 S44

Ryjf285 at 45C 3.932 4.012 3.971 2.045 6.305 4.659 2.664 2.324 4.593 1.352 4.207 4.019 4.188 4.876 13.5309 8.9377 8.9198 8.4277 8.2134 7.7925 7.7752 7.4691 7.4511 7.4321 7.2930 7.2721 7.2598 7.2400 7.1848 7.1742 7.1725 7.0251 7.0079 6.9900 4.0763 4.0544 4.0323 3.8852 3.8649 3.8448 3.5806 3.5632 3.5435 3.5231 1.5790 1.5647 12.36 11.97 0.6670 0.6530 0.5269 0.5110 PPM 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 file: F:\MR for paper 1\Done\Ryjf285\45C\fid expt: <zg30> transmitter freq.: 400.172471 Mz width: 8250.83 z = 20.618173 ppm = 0.125898 z/pt number of scans: 64 freq. of 0 ppm: 400.170015 Mz LB: 0.300 GB: 0.0000 S45

163.0352 162.0527 150.2201 150.1158 148.8876 139.6187 134.3190 132.2769 132.0393 129.0610 128.8750 128.5539 128.0765 126.9052 125.3587 124.0021 123.8817 122.6486 120.6032 114.7340 112.8283 77.3142 76.9964 76.6789 72.6108 68.8046 32.5156 18.5970 17.7421 (S) (S) (R) (S) (S) PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 file: F:\MR for paper 1\Syjf285 Pure\3\fid expt: <zgpg30> transmitter freq.: 100.622830 Mz width: 23980.82 z = 238.323802 ppm = 0.365918 z/pt number of scans: 9808 freq. of 0 ppm: 100.612771 Mz LB: 1.000 GB: 0.0000 S46

added more Rh(CD)SbF6 128.8546 127.1810 Ph Ph P P Ph Ph Rh SbF 6 PPM 144.0 140.0 136.0 132.0 128.0 124.0 120.0 116.0 112.0 108.0 104.0 file: G:\yjf106PPRh V\1\fid expt: <zgpg30> transmitter freq.: 101.249405 Mz width: 64516.13 z = 637.200082 ppm = 0.984438 z/pt number of scans: 180 freq. of 0 ppm: 101.254467 Mz LB: 1.000 GB: 0.0000 S47

Me Me 141.4502 140.3410 Ph 2 P Rh P Ph 2 Me SbF 6 Me 141.2704 141.2155 140.1548 140.1064 room temp. 45 o C back to room temp. PPM 143.6 143.2 142.8 142.4 142.0 141.6 141.2 140.8 140.4 140.0 139.6 139.2 138.8 138.4 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf157PPRh\6\fid expt: <zgpg30> transmitter freq.: 161.967474 Mz width: 64935.06 z = 400.914228 ppm = 0.990830 z/pt number of scans: 72 freq. of 0 ppm: 161.975573 Mz LB: 1.000 GB: 0.0000 S48

0.995 0.438 1.085 0.408 134.1236 133.9118 132.4306 132.2189 Ph 2 P P Ph 2 Rh SbF 6 PPM 139.0 138.0 137.0 136.0 135.0 134.0 133.0 132.0 131.0 130.0 129.0 128.0 127.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf276PPIIRh\1\fid expt: <zgpg30> transmitter freq.: 101.249405 Mz width: 64516.13 z = 637.200082 ppm = 0.984438 z/pt number of scans: 152 freq. of 0 ppm: 101.254467 Mz LB: 1.000 GB: 0.0000 S49

0.994 0.134 0.986 0.130 134.0627 133.7545 132.3557 132.0597 Ph 2 P P Ph 2 Rh SbF 6 PPM 138.0 137.0 136.0 135.0 134.0 133.0 132.0 131.0 130.0 129.0 128.0 127.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274IIPPRh\1\fid expt: <zgpg30> transmitter freq.: 101.249405 Mz width: 64516.13 z = 637.200082 ppm = 0.984438 z/pt number of scans: 213 freq. of 0 ppm: 101.254467 Mz LB: 1.000 GB: 0.0000 S50

0.987 0.968 135.2355 133.5571 Ph 2 P Rh SbF P 6 Ph 2 PPM 150.0 148.0 146.0 144.0 142.0 140.0 138.0 136.0 134.0 132.0 130.0 128.0 126.0 124.0 122.0 120.0 118.0 file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf285PPRh\3\fid expt: <zgpg30> transmitter freq.: 101.249405 Mz width: 64516.13 z = 637.200082 ppm = 0.984438 z/pt number of scans: 234 freq. of 0 ppm: 101.254467 Mz LB: 0.300 GB: 0.0000 S51