Folding-Driven Asymmetric Induction of a Catalytic Dendrimer

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1 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 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

2 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

3 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

4 Figure 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 ( 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

5 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 o C. 1 -MR(400Mz, CDCl 3 ): δ 4.84 p.p.m.(s, 4), 7.14 (t, J = 7.6 z, 2), (m, 4), (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 , , , , , , , , , RMS(m/z): [M+K] + calcd for C K 2, ; found, 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 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), (m, 4), 7.24 (m, 6), (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 , , , , , , , , , , , , , MALDI(m/z): [M+a] + calcd for C a +, ; found, 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 o C; 1 -MR (400 Mz, CDCl 3 ): δ 1.11 p.p.m. (d, J = 6.4 z, 6), 3.18 S5

6 (s, 6), 3.30 (dd, J = 10.5, 4.2 z, 2), 3.36 (dd, J = 10.6, 5.7 z, 2), (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), (s, 2). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , 74.58, 70.35, 58.93, RMS (m/z): [M+a] + calcd for C a +, ; found, (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 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), (m, 1), 3.99 (t, J = 8.0 z, 1), (m, 1), (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 , , , , , , , 72.86, 68.71, 33.15, 18.92, RMS (m/z): [M+] + calcd for C , ; found, 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 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), (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), (s, 2). 13 C-MR (100 Mz, S6

7 CDCl 3 ): δ , , , , , , , , , , , 72.35, 61.70, MALDI (m/z): [M+] + calcd for C , ; found, 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 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), (m, 2), (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), (s, 2). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , , 72.56, 69.16, 32.89, 18.17, MALDI (m/z): [M+a] + calcd for C a +, ; found, 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

8 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, 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 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), (m, 4), (m, 4), (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), (s, 4). 13 C-MR ( Mz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , , , 75.62, 74.65, 70.27, 58.93, MALDI (m/z): [M+a] + calcd for C a +, ; found, 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

9 (0.49 g, 96%). M.p o C 1 -MR (400 Mz, CDCl 3 ): δ 1.13 p.p.m. (d, J = 6.2 z, 12), 3.17(s, 12), (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), (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , 74.70, 70.32, 58.91, MALDI (m/z): [M] + calcd for C , ; found, 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 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), (m, 4), 4.25 (t, J = 8.4 z, 4), 4.41 (s, 4), (m, 4), (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), (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), (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , , 75.75, 72.78, 62.11, MALDI (m/z): [M+a] + calcd for C a +, ; found, S9

10 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 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), (s, 2), (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), (s, 4). 13 C-dept135 MR (125.7 Mz, CDCl 3 ): δ , , , , , , , , 72.90, 62.28, 30.91, MALDI (m/z): [M+a] + calcd for C a ; found, 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

11 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 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), (m, 4), (m, 4), 3.86 (t, J = 8.2 z, 4), 4.12 (t, J = 8.5 z, 4), 4.40 (s, 4), (m, 4), (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), (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , , , 75.64, 72.70, 69.19, 32.98, 18.30, MALDI (m/z): [M+a] + calcd for C a +, ; found, ,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 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), (m, 4), (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), (s, 4). 13 C-MR (100 Mz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , 72.57, 68.82, 32.60, 18.43, MALDI (m/z): [M+a] + calcd for C a +, ; found, S11

12 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 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), (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), (m, 4), (m, 6), 7.15 (t, J = 7.5 z, 4), 7.42 (d, J = 5.7 z, 4), (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), (s, 4). 13 C-MR (62.9 Mz, CDCl 3 ): , , , , , , , , , , , , , , , , , , , , , , , , , 75.41, 72.57, 69.13, 32.91, 18.20, MALDI (m/z): [M+a] + calcd for C a +, ; found, S12

13 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 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), (s, 4). 13 C-MR (100 Mz, CDCl 3 ): , , , , , , , , , , , , , , , , , , , , , 72.62, 68.81, 32.52, 18.60, MALDI (m/z): [M+a] + calcd for C a +, ; found, 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 ( 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 B. In a drybox, (S)-2,2'-bis(diphenylphosphinooxy)-1,1'-binaphthyl (20 mg, 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, mmol) in C 2 Cl 2 (0.2 ml) at S13

14 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 (d, J P-Rh = 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, mmol) and DMAP (20 mg, 2.1 e.q.) in TF (1 ml), Ph 2 PCl (0.029 ml, 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 , B. Compound SI 9 (26.5 mg, mmol) in C 2 Cl 2 (0.2 ml) was added slowly to a solution of Rh + (CD) 2 SbF 6 - (8.9 mg, 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 (d, J P-Rh = 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

15 dine-2,6-dicarboxamide) (SI 12) (75.8 mg, mmol) and DMAP (16.9 mg, 2.1 e.q.) in TF (0.4 ml) was added Ph 2 PCl ( ml, 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 , B. To a solution of Rh + (CD) 2 SbF 6 - (10.5 mg, mmol) in C 2 Cl 2 (0.2 ml), compound SI 14 (28.8 mg, 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 (d, J P-Rh = z), (d, J P-Rh = 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, mmol) and DMAP (8.9 mg, 2.1 e.q.) in TF (0.4 ml) was added Ph 2 PCl ( ml, 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 , B. To a solution of Rh + (CD) 2 SbF 6 - (15.7 mg, mmol) in C 2 Cl 2 (0.2 ml), compound SI 15 (46.3 mg, 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 (d, J P-Rh = z), (d, J P-Rh = z).. S15

16 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, mmol) in dry TF (0.5 ml) and DMAP (16.6 mg, 2.05 eq.), Ph 2 PCl (0.024 ml, 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 B. To a stirred solution of Rh + (CD) 2 SbF 6 - (5.6 mg, mmol) in C 2 Cl 2 (0.2 ml), compound SI (R)-18 (17.5 mg, 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 (d, J P-Rh = 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 ( 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

17 References 1. Alexakis, Alexandre; Polet, Damien; Rosset, Stephane; March, Sebastien. J. rg. Chem. 2004, 69, Xu, Yingjian; Clarkson, Guy C.; Docherty, Gordon; orth, Carl L.; Woodward, Gary; Wills, Martin. J. rg. Chem. 2005, 70, 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, Kurosu, Michio; Lin Mei-uey; Kishi Yoshito, J. Am. Chem. Soc. 2004, 126, Preston, Adam J.; Fraenkel, Gideon; Chow, Albert; Gallucci, Judith C.; Parquette, Jon R.. J. rg. Chem. 2003, 68, Clyne, D. S., Mermet-Bouvier, Y. C., omura,. & RajanBabu, T. V. J. rg. Chem. 64, (1999). 7. Zhang, F.Y.; Kwok W..; Chan Albert S.C., Tetrahedron: Asymmetry 2001, 12, RajanBabu T.V.; Ayers T.A.; alliday G.A.; You K.K.; Calabrese J.C. J. rg. Chem. 1997, 62, S17

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

19 Bn Bn PPM file: F:\MR for paper 1\Done\yjf104-1\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 21 freq. of 0 ppm: Mz LB: GB: S19

20 Bn Bn PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf104-1\3\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 178 freq. of 0 ppm: Mz LB: GB: S20

21 Bn Bn PPM file: Z:\jyu\MR total\2007\yjf283\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 10 freq. of 0 ppm: Mz LB: GB: S21

22 Bn Bn PPM file: Z:\jyu\MR total\2007\yjf283\2\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 89 freq. of 0 ppm: Mz LB: GB: S22

23 Me Me PPM file: F:\MR for paper 1\Done\yjf92\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 17 freq. of 0 ppm: Mz LB: GB: S23

24 Me Me PPM file: F:\MR for paper 1\yjf92\2\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 290 freq. of 0 ppm: Mz LB: GB: S24

25 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf11B\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 22 freq. of 0 ppm: Mz LB: GB: S25

26 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf11B\2\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 105 freq. of 0 ppm: Mz LB: GB: S26

27 PPM file: G:\yjf13C\proton\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 26 freq. of 0 ppm: Mz LB: GB: S27

28 PPM file: G:\yjf13C\carbon\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 72 freq. of 0 ppm: Mz LB: GB: S28

29 PPM file: F:\MR for paper 1\BW-III-51\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 138 freq. of 0 ppm: Mz LB: GB: S29

30 PPM file: F:\MR for paper 1\Done\yjf12B\2\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 16 freq. of 0 ppm: Mz LB: GB: S30

31 Me Me x Bn Bn Me Me PPM file: F:\MR for paper 1\Done\yjf156-1\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 20 freq. of 0 ppm: Mz LB: GB: S31

32 Me Me Bn Bn Me Me PPM file: F:\MR for paper 1\Done\yjf156-1\3\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 1696 freq. of 0 ppm: Mz LB: GB: S32

33 Me Me Me Me PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf157 pure again\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 27 freq. of 0 ppm: Mz LB: GB: S33

34 Me Me Me Me PPM file: F:\MR for paper 1\Done\yjf157 pure again\3\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 831 freq. of 0 ppm: Mz LB: GB: S34

35 Bn Bn PPM file: F:\MR for paper 1\Done\yjf276-1 new\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 128 freq. of 0 ppm: Mz LB: GB: S35

36 Bn Bn PPM file: C:\Documents and Settings\jianfengyu yu\desktop\yjf276-1c\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: freq. of 0 ppm: Mz LB: GB: S36

37 PPM file: C:\Documents and Settings\jianfengyu yu\desktop\check yjf276\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 18 freq. of 0 ppm: Mz LB: GB: S37

38 PPM file: Z:\jyu\MR total\check yjf276\2\fid expt: <dept135> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 57 freq. of 0 ppm: Mz LB: GB: S38

39 Bn Bn PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274-1\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 128 freq. of 0 ppm: Mz LB: GB: S39

40 Bn Bn PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274-1\2\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: freq. of 0 ppm: Mz LB: GB: S40

41 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274C\2\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 66 freq. of 0 ppm: Mz LB: GB: S41

42 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274C\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 344 freq. of 0 ppm: Mz LB: GB: S42

43 (R) Bn Bn (S) (S) (S) (S) PPM file: F:\MR for paper 1\Syjf286 pure\1\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 16 freq. of 0 ppm: Mz LB: GB: S43

44 Bn Bn PPM file: F:\MR for paper 1\Done\Syjf286 pure\3\fid expt: <zgpg30> transmitter freq.: Mz time domain size: points width: z = ppm = z/pt number of scans: 183 freq. of 0 ppm: Mz LB: GB: S44

45 Ryjf285 at 45C PPM file: F:\MR for paper 1\Done\Ryjf285\45C\fid expt: <zg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 64 freq. of 0 ppm: Mz LB: GB: S45

46 (S) (S) (R) (S) (S) PPM file: F:\MR for paper 1\Syjf285 Pure\3\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 9808 freq. of 0 ppm: Mz LB: GB: S46

47 added more Rh(CD)SbF Ph Ph P P Ph Ph Rh SbF 6 PPM file: G:\yjf106PPRh V\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 180 freq. of 0 ppm: Mz LB: GB: S47

48 Me Me Ph 2 P Rh P Ph 2 Me SbF 6 Me room temp. 45 o C back to room temp. PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf157PPRh\6\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 72 freq. of 0 ppm: Mz LB: GB: S48

49 Ph 2 P P Ph 2 Rh SbF 6 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf276PPIIRh\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 152 freq. of 0 ppm: Mz LB: GB: S49

50 Ph 2 P P Ph 2 Rh SbF 6 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf274IIPPRh\1\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 213 freq. of 0 ppm: Mz LB: GB: S50

51 Ph 2 P Rh SbF P 6 Ph 2 PPM file: C:\Documents and Settings\jianfengyu yu\my Documents\MR for paper 1\yjf285PPRh\3\fid expt: <zgpg30> transmitter freq.: Mz width: z = ppm = z/pt number of scans: 234 freq. of 0 ppm: Mz LB: GB: S51