J. Am. Chem. Soc., 1998, 120(41), , DOI: /ja982683c

Transcription

1 J. Am. Chem. Soc., 1998, 120(41), , DOI: /ja982683c Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machinereadable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at Copyright 1998 American Chemical Society

2 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page 1 Cooperative Asymmetric Catalysis Using Dimeric Salen Complexes Reed G. Konsler, Jarn Karl, and Eric N. Jacobsen* Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts Supporting Information General: All reactions were conducted in standard glassware with magnetic stirring under an atmosphere of dry nitrogen. Ethereal solutions of hydrazoic acid were prepared from sodium azide/sulfuric acid, dried over sodium sulfate, and distilled from anhydrous phosphoric acid prior to use.' The concentration of each preparation was determined by quenching an aliquot with aqueous potassium hydroxide and titrating with aqueous hydrochloric acid. Enantiomeric excess of the ARO product trans-1-azido-2- cyclopentanol was determined by GC analysis of the trimethylsilyl ether derivative using the commercially available Cylcodex-B chiral column (30m x 0.25mm id x 0.25Iim film; J&W Scientific, 750 isothermal, RR-enantiomer Rt: min, S,S-enantiomer Rt: mm). (RR)-Pyrrolidine Salen Ligand 6: Palladium on H carbon (10% w/w, 0.55 g, 0.26 mmol) was added to a solution of (3R,4R)-1-benzyl-3,4- H 4 -P "H bis(azido)pyrrolidine 2 (1.50 g, 6.17 mmol) in ethanol N N- / trifluoroacetic acid (20 ml, 4:1). The suspension was shaken under 6 atm hydrogen for 16 hrs, filtered tbu OH HO / \ tbu through Celite, and concentrated under vacuum. The - crude residue was dissolved in ethanol / water (50 tbu 6 tbu ml, 9:1) and neutralized with potassium carbonate (3.00 g, mmol). Neat 3,5-di-tertbutylsalicylaldehyde (3.18 g, mmol) was added at once and the reaction was heated to reflux for 2 hours. The reaction mixture was then poured into 100 ml brine and extracted with dichloromethane (3 x 50 ml). The organic phases were combined and washed with brine (50 ml), dried over sodium sulfate, and concentrated. The product was purified by silica gel chromatography (ether / hexane, 2:1) to give 2.33g (71% yield) as a foamy yellow glass. IR (film) 2959, 2907, 2869, 1625, 1596, 1468, 1439 cm; 1 H- NMR (500 MHz, CDCl 3 ) (s, 2H), 8.34 (s, 2H), 7.39 (d, J= 2.0, 2H), 7.06 (d, J= 2.0, 2H), 3.90 (dd; J= 4.8, 4.8; 2HI, 3.51 (dd; J= 11.9, 4.8; 2H), 3.17 (dd; J= 11.9, 4.8; 2H), 1.42 (s, 18H), 1.29 (s, 18H); 1 C-NMR (500 MHz, CDCL 3 ) , 166.3, 157.8, 140.4, 136.7, 127.3, 126.2, 117.7, 54.8, 35.0, 34.1, 31.4, 29.4 HRMS (FAB) calcd for [C 3 4 H 5 1 N H]+ = , found nbu (RR)-N-n-Rutyl Pyrrolidine Salen Ligand 7: 1 Intermediate 6 (0.500 g, 0.94 mmol), bromobutane N (0.200 ml, 2.00 mmol), diisopropylethylamine H-P -- ( ml, 3.00 mmol), and toluene (1.00 ml) were N H combined in a vial equipped with a stirbar and ~N N wrapped in aluminum foil. The reaction mixture was tu OH / stirred at 1000 C for 12 hrs and then concentrated Bu OH HO Bu under vacuum. The residue was purified by silica gel t- chromatography (EtOAc / Hexane, 1:19) to give 7 7 Be (500 mig, 90% yield) as a foamy yellow glass. R S-1

3 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page 2 (film) 2958, 2911, 2871, 1626, 1596, 1468, 1440 cm'; 1 H-NMR (500 MHz, CDC1 3 ) (s, 2H), 8.30 (s, 2H), 7.38 (d, J= 2.0, 2H), 7.04 (d, J= 2.0, 2H), 3.96 (dd; J= 5.1, 5.1; 2H), 3.09 (dd; J=9.5, 5.1; 2H), 2.93 (dd; J= 9.5, 5.1; 2H), 2.58 (m, 1H), 2.46 (i, 1H), 1.52 (in, 2H), 1.43 (s, 18H), 1.40 (in, 2H), 1.27 (s, 18H), 0.94 (t, J= 7.3, 3H); C- NMR (500 MHz, CDCl 3 ) , 158.0, 140.3, 136.7, 127.2, 126.3, 117.7, 75.4, 60.9, 56.2, 35.1, 34.2, 31.5, 30.1, 29.5, 20.8, 14.1; HRMS (FAB) calcd for [C 38 H 57 N H] = , found (RR)-Pyrrolidine Dimeric Salen Ligand 8: 2 Intermediate 6 (0.500 g, 0.94 mmol), 1,10- N dibromodecane (0.120 g,.40 mmol), diisopropylethylamine H (0.145 ml, 3.00 mmol), and toluene (2.00 ml) were combined in a vial N N equipped with a stirbar and wrapped in aluminum foil. The reaction was stirred at 900 C for 36 hrs tbu OH HO \ Bu and then concentrated under vacuum. The residue was punfied by silica gel chromatography (EtOAc / Bu 8 tbu Hexane, 1:19) to afford 8 (390 mg, 69% 'ield) as a foamy yellow glass. IR (film) 2958, 2908, 2868, 1625, 1596, 1468, 1440 cm ; H-NMR (500 MHz, CDC1 3 ) (s, 4H), 8.30 (s, 4H), 7.37 (d, J= 2.0, 4H), 7.04 (d, J= 2.0, 4H), 3.96 (m, 4H), 3.09 (in, 4H), 2.93 (in, 4H, 2.57 (m, 2H), 2.45 (in, 2H), 1.50 (m, 4H), 1.45 (s, 36H), 1.33 (in, 12H), 1.27 (s, 36H); C-NMR (500 MHz, CDC1 3 ) , 158.0, 140.3, 136.7, 127.2, 126.3, 117.7, 75.4, 60.8, 56.5, 46.5, 35.1, 34.2, 31.5, 29.7, 29.5, 28.7, 27.6; HRMS (FAB) calcd for [C 78 H 12 0 N H]+ = 1205, found General Procedure for the Preparation of Pyrrolidine (salen)cr"'-cl Complexes 2 and 3: THF (10ml) was added to a mixture of chromium(ii) chloride (185 mg, 1.50 mmol) and monomeric ligand 7 (1.00 mmol) or dimeric ligand 8 (0.50 mmol). The mixture was stirred under nitrogen for 6 h and saturated aqueous ammonium chloride (10 ml) was added. The mixture was stirred under air for 6 h and diluted with tert-butyl methyl ether (25 ml). The aqueous layer was removed and the organic layer was washed with saturated ammonium chloride (25 ml x 4) and brine (25 ml x 2), dried over sodium sulfate, concentrated under vacuum, and dried by azeotropic distillation with benzene (3 x 5 ml) to give the product as a brown solid (81-92% yield). (R)-Pyrrolidine Dimer 2: Mp (open capillary) 'C (dec), IR: (film) 2954, 2867, 1631, 1531, 1461, 1437 cm-'; MS (FAB) calcd for [C 7 8H Cr 2 Cl 2 N C1] = 1304, found (R)-N-butyl Monomer 3: Mp (open capillary) 'C (dec), IR: (film) 2958, 2908, 2871, 1631, 1531, 1463, 1437 cm- 1 ; MS (FAB) calcd for [C 3 8 H 5 7 CrC1N Cl]= , found tert-butyl-2,5-dihydroxybenzaldehyde: A tetrabutylammonium flouride solution (1.0 M in THF, 30.5 ml, 30.5 mmol, Aldrich) was added dropwide to a solution of 3-tert-butyl-2-hydroxy-5- HO )/OH triisopropylsiloxybenzaldehyde 3 (9.0 g, 25.4 mmol) in 60 ml THF at -78 'C and allowed to warm to room temperature over 3 h. The tbu reaction mixture was poured into 100 ml water and extracted (100 ml x 3) with diethyl ether. The organic layers were combined, washed with saturated aqueous ammonium chloride (100 ml x 2), dried over magnesium sulfate and concentrated. The product was purified by silica gel chromatography (diethyl ether/hexanes, 1:4) to give 3.5 g (71% yield) product as a yellow solid. Mp (open capillary) oc; IR (KBr) 3400(b), 2968, 2877, 1596, 1645, 1589, 1495, 1263, S-2

4 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page cm 1 ; 'H-NMR (500 MHz, CDC1 3 ) (s, 1H), 7.22 (d, J = 1.6 Hz, 1H), 7.13 (d, J = 1.4 Hz, 1H), 1.52 (s, 9H) "C-NMR (500 MHz, CDC1 3 ) , 153.1, 149.6, 138.4, 122.9, 115.4, 101.8, 34.4, 28.9; HRMS (FAB) caled for C 11 H Si [M] , found Dissymmetric Salen Ligand 9: Ethanol (240mL) was added to a solution of potassium carbonate (13.0 Hm- -IH g, 94.0 mmol) and (R)-1,2-diammoniumcyclohexane N N- mono-(+)-tartrate salt (12.5 g, 47.0 mmol) in distilled water (60 ml). The reaction mixture was Bu \ heated to reflux for 30 min and a solution of 3,5-ditu /OH HO / OH tert-butylsalicylaldehyde (11.0 g, 47.0 mmol) and 3- tert-butyl-2,5-dihydroxybenzaldehyde (10.0 g, 51.7 tbu 9 tbu mmol) in THF (80 ml) was added over 30 mm. The reaction mixture was allowed to cool to room temperature over 4 h and dried over sodium sulfate. The mixture of salen ligands was separated by silica gel chromatography (gradient elution: diethyl ether /hexanes, 1:20 to 1:1) to give 9 (10.1 g, 42% yield) of as a foamy yellow glass. IR (film) 3316 (b), 2954, 2864, 1630, 1598, 1465, 1440 cm;,h- NMR (500 MHz, CDCl 3 ) (s, 1H), 8.12 (s, 1H), 7.42 (d, J 2.3, 1H), 7.05 (d, J= 2.3, 1H), 6.87 (d, J= 2.3, 1H), 6.44 (d, J= 2.3, 1H), 3.29 (m, 2H), 1.89 (in, 4H), 1.71 (in, 4H), 1.52 (s, 9H), 1.42 (s, 9H), 1.32 (s, 9H); 13C-NMR (500 MHz, CDC1 3 ) , 165.2, 158.9, 154.6, 147.0, 140.0, 138.6, 136.8, 127.3, 126.2, 118.4, 118.3, 117.8, 114.9, 72.1, 72.0, 35.1, 34.9, 34.1, 33.2, 33.0, 31.7, 31.5, 29.6, 29.4, 24.3; HRMS (FAB) calcd for [C 3 2 H 4 6 N H] = , found H Q,1H HQ-H N N O O N N t Bu OH HO / O> $ O OH HO t Bu tbu tbu 1Oa-g tbu tbu General Procedure for the Preparation of Dimeric Ligands 10a-g: Diacid chloride (1.00 mmol) was added to a solution of 9 (1.01 g, 2.00 mmol), triethylanine (0.42 ml, 3.00 mmol) and 4-(dimethylamino)-pyridine (24.0 mg, 0.20 mmol) CH 2 Cl 2 (10 ml) at 0 oc. The reaction was stirred for 6 h, diluted with diethyl ether (40 ml), washed with IN aqueous HCI (50 ml x 2), saturated aqueous sodium bicarbonate (50 ml x 2), and brine (50 ml x 2). The solution was concentrated under vacuum and purified by silica gel chromatography (diethyl ether /hexanes, 1:19) to afford 10 as a foamy yellow glass in 64-95% yield. (R,R)-Ligand 10a (n=2): Yield: 65%. IR (film) 2954, 2866, 1758, 1630, 1596, 1466, 1440 cm-'; 'H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.31 (s, 2H), 8.22 (s, 2H), 7.32 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.92 (d, J= 2.4, 2H), 6.77 (d, J= 2.4, 2H), 3.33 (in, 4H), 2.91 (s, 4H), 1.88 (in, 8H), 1.73 (in, 4H), 1.45 (in, 4H), 1.40 (s, 18H), 1.37 (s, 18H), 1.24 (s, 18H); 13 C-NMR (500 MHz, CDC1 3 ) , 165.9, 164.6, 158.3, 158.0, 141.5, 140.0, 138.7, 136.5, 127.0, 126.0, 122.7, 121.3, 118.3, 117.8, 72.6, 72.2, S-3

5 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page , 34.9(44), 34.8(91), 34.1, 33.3, 33.2(34), 33.1(61), 31.5, 29.5, 29.2, 24.3; MS (FAB) calcd for[c 6 8 H 9 4 N H]* = 1095, found (R,R)-Ligand 10b (n=4): Yield: 85%. IR (film) 2953, 2865, 1758, 1630, 1596, 1466, 1439 cmg; H-NMR (500 MHz, CDC1 3 ) (s, 2H), (s, 2H), 8.31 (s, 2H), 8.22 (s, 2H), 7.32 (d, J= 2.5, 2H), 6.98 (d, J= 2.4, 2H), 6.93 (d, J= 2.5, 2H), 6.76 (d, J= 2.4, 2H), 3.33 (m, 4H), 2.56 (m, 4H), 1.88 (m, 8H), 1.83, J= 3.4, 4H), 1.73 (m, 4H), 1.47 (m, 4H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (s, 18H); C-NMR (500 MHz, CDC1 3 ) , 165.9, 164.7, 158.2, 158.0, 141.5, 140.0, 138.6, 136.4, 127.0, 126.0, 122.8, 121.4, 118.3, 117.8, 72.5, 72.3, 35.0, 34.9, 34.1, 33.9, 33.3(33), 33.2(59), 33.1(79), 31.4, 29.5, 29.2, 24.4, 24.3; MS (FAB) calcd for[c 7 oh 9 8 N H]+ = 1123, found (R,R)-Ligand 10c (n=5): Yield: 90%. IR (film) 2955, 2865, 1759, 1630, 1596, 1467, 1439 cmi; 1 H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.21 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.97 (d, J= 2.4, 2H), 6.91 (d, J= 2.4, 2H), 6.75 (d, J= 2.4, 2H), 3.32 (m, 4H), 2.52 (t, J= 6.4, 4HJ 1.89 (m, 8H), 1.76 (m, 8H), 1.46 (m, 6H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (s, 18H); C-NMR (500 MHz, CDCl 3 ) , 166.0, 164.7, 158.2, 158.0, 142.0, 140.0, 138.6, 136.4, 127.0, 126.0, 122.8, 121.4, 118.3, 117.8, 72.5, 72.3, 35.0(17), 34.9(60), 34.1 (2C), 33.3, 33.2, 31.5 (2C), 29.5, 29.2, 28.6, 24.6, 24.3; MS (FAB) calcd for[c 7 lhioon408 +H]+ = 1137, found (R,R)-Lig and10d(n=6): Yield: 95%. IR (film) 2954, 2864, 1758, 1630, 1596, 1468, 1439 cm- 1 'H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.23 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.92 (d, J= 2.4, 2H), 6.76 (d, J= 2.4, 2H), 3.32 (m, 4H), 2.56 (t, J= 6.5, 4 HJ (m, 8H), 1.74 (m, 8H), 1.45 (m, 8H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (s, 18H); C-NMR (500 MHz, CDC1 3 ) , 165.9, 164.7, 158.2, 158.0, 141.6, 140.0, 138.7, 136.4, 127.0, 126.0, 122.8, 121.4, 118.3, 117.8, 72.5, 72.3, 35.0, 34.9, 34.3, 34.1, 33.3, 33.2, 31.6, 31.5, 29.5, 29.2, 28.8, 24.8, 24.3; MS (FAB) caled for[c 72 HI 0 2 N 4 0s +H]+ = 1151, found (S,S)-Ligand 10d (n=6): Yield: 95%. IR (film) 2955, 2864, 1758, 1630, 1596, 1468, 1439 cm- 1 ; 1 H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.23 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.92 (d, J= 2.4, 2H), 6.76 (d, J= 2.4, 2H), 3.32 (m, 4H), 2.56 (t, J= 6.5, 4 H) 1.92 (m, 8H), 1.74 (m, 8H), 1.45 (m, 8H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (s, 18H); C-NMR (500 MHz, CDCl 3 ) , 165.8, 164.7, 158.2, 158.0, 141.6, 140.0, 138.7, 136.4, 126.9, 126.0, 122.8, 121.4, 118.3, 117.8, 72.5, 72.3, 35.0, 34.9, 34.3, 34.1, 33.3, 33.2, 31.6, 31.5, 29.5,.29.2, 28.8, 24.8, 24.3; MS (FAB) caled for[c 7 2 HIO 2 N 4 0s +H] = 1151, found (R,R)-Ligand 10e (n=7): Yield: 90%. IR (film) 2956, 2865, 1758, 1630, 1596, 1467, 1439 cm-; 1 1H-NMR (500 MHz, CDC1 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.23 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.91 (d, J= 2.4, 2H), 6.75 (d, J= 2.4, 2H), 3.32 (m, 4H), 2.50 (t, J= 6.4, 4H), 1.98 (m, 8H), 1.72 (m, 8H), 1.45 (m, 8H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (m, 20H); 13 C-NMR (500 MHz, CDCl 3 ) , 165.9, 164.7, 158.2, 158.0, 141.6, 140.0, 138.6, 136.4, 127.0, 126.0, 122.8, 121.4, 118.3, 117.8, 72.5, 72.3, 35.0, 34.9, 34.3, 34.1, 33.3, 33.2, C), 29.5, 28.9(93), 28.9(66), 24.9, 24.3, 22.7; MS (FAB) calcd for[c 73 HIo 4 N 4 0s +H] = 1165, found (R,R)-Ligand 10f(n=8): Yield: 83%. IR (film) 2953, 2862, 1759, 1630, 1596, 1467, 1439 cm'; 1 H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.23 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.92 (d, J= 2.4, 2H), 6.75 (d, J= 2.4, 2H), 3.32 (m, 4H), 2.50 (t, J= 6.4, 4H), 1.91 (m, 8HJ 1.70 (m, 8H), 1.45 (m, 8H), 1.41 (s, 18H), 1.38 (s, 18H), 1.24 (m, 18H), 1.22 (s, 4H); C-NMR (500 MHz, CDCl 3 ) 6 S-4

6 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page , 165.9, 164.7, 158.1, 157.9, 141.6, 140.0, 138.5, 136.4, 126.9, 126.0, 122.8, 121.4, 118.2, 117.8, 72.5, 72.2, 34.9(44), 34.8(89), 34.3, 34.0, 33.2, 33.1, 31.4 (2C),'29.4, 29.1(49), 29.0(89), 27.0, 24.9, 24.3; MS (FAB) caled for[c 74 H 1 06 N H]* = 1179, found (R,R)-Ligand 10g (n=10): Yield: 64%. IR (film) 2954, 2862, 1759, 1631, 1596, 1469, 1439 cm' ; 'H-NMR (500 MHz, CDCl 3 ) (s, 2H), (s, 2H), 8.30 (s, 2H), 8.23 (s, 2H), 7.31 (d, J= 2.4, 2H), 6.98 (d, J= 2.4, 2H), 6.91 (d, J= 2.4, 2H), 6.75 (d, J= 2.4, 2H), 3.32 (in, 4H), 2.49 (t, J= 6.4, 4H), 1.91 (in, 8H), 1.71 (in, 8H), 1.45 (in, 8H), 1.41 (s, 18H), 1.38 (s, 18H), 1.33 (in, 6H), 1.24 (in, 18H); 13 C-NMR (500 MHz, CDC1 3 ) , 165.9, 164.7, 158.1, 157.9, 141.6, 140.0, 138.5, 136.4, 126.9, 126.0, 122.8, 121.4, 118.2, 117.8, 72.5, 72.2, 34.9(44), 34.8(72), 34.3, 34.0, 33.2, 33.1, 31.5 (2C), 31.4, 29.4, 29.2, 29.1, 25.0, 24.3, 22.6; MS (FAB) calcd for [C 76 HI on H]+ = 1207, found (R)-Acetate Ligand 11: Acetyl chloride (2.00 mmol) was added to a solution of 9 (1.01 g, 2.00 H 'H mmol), triethylamine (0.42 ml, 3.00 mmol) and 4- -N N- (dimethylamino)-pyridine (24.0 mg, 0.20 mmol) CH 2 Cl 2 (10 ml) at 0 oc. The reaction was stirred tbu \ OH HO / OAc for 6 h, diluted with diethyl ether (40 ml), and O_ c washed with 1N aqueous HC1 (50 ml x 2), tbu 11 tbu saturated aqueous sodium bicarbonate (50 ml x 2), and brine (50 ml x 2). The solution was concentrated under vacuum and purified by silica gel chromatography (diethyl ether /hexanes, 1:19) to afford 11 (796 mg, 73 % as a foamy yellow glass. IR (film) 2956, 2864, 1762, 1631, 1596, 1469, 1439 cm-; H-NMR (500 MHz, CDCl 3 ) (s, 1H), (s, 1H), 8.30 (s, 1H), 8.23 (s, 1H), 7.32 (d, J= 2.5, 1H), 6.98 (d, J= 2.5, 1H), 6.93 (d, J= 2.5, 1H), 6.76 (d, J= 2.5, 1H), 3.33 (in, 2H), 2.24 (s 3H), 1.92 (in, 4H), 1.73 (in, 2H), 1.48 (in, 2H), 1.41 (s, 9H), 1.39 (s, 9H), 1.25 (s, 9H); 3C-NMR (500 MHz, CDCl 3 ) , 165.9, 164.6, 158.2, 157.9, 141.5, 140.0, 138.6, 136.4, 126.9, 126.0, 122.8, 121.4, 118.2, 117.8, 72.5, 72.3, 34.9(44), 34.9(03), 34.0, 33.2, 33.1, 31.4, 29.4, 29.1, 24.3, 22.7, 21.0; HRMS (FAB) caled for [C 34 H 48 N H]+ = , found General Procedure for the Preparation of (salen)crl"-n 3 Dimers 4a-g and Monomeric Analog 5: THF (20ml) was added to a mixture of chromium(l) chloride (369 mg, 3.00 mmol) and ligand dimer (1.00 mmol). The mixture was stirred under nitrogen for 6 h and saturated aqueous ammonium chloride (20 ml) was added. The mixture was stirred under air for 6 h and diluted with diethyl ether or tert-butyl methyl ether (50 ml). The aqueous layer was removed and the organic layer washed with saturated aqueous ammonium chloride (30 ml x 4) and brine (30 ml x 3), dried over sodium sulfate and concentrated to give a brown solid. This solid was dissolved in tertbutyl methyl ether / THF (40 ml, 1:1). To this solution was added silver tetrafluroborate (428 mg, 2.20 mmol). After 4 h stirring the mixture was filtered through Celite with tertbutyl methyl ether/thf (40 ml, 1:1) and sodium azide (260 mg, 4.00 mmol) was added. After stirring 12 hrs the reaction mixture was washed with water (50 ml x 3) and brine (50 ml x 2), dried over sodium sulfate, filtered through Celite, and concentrated to give a brown solid. This solid was suspended in a solution of azidotrimethyl silane (1.32 ml, mmol) in tert-butyl methyl ether (5 ml). After 10 h the solution was filtered under an atmosphere of nitrogen, the solids triturated and washed with tert-butyl methyl ether (4 x 10 ml), and dried under vacuum for 6 h at room temperature to give 48-75% yield of catalyst as a fine brown powder. S-5

7 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page 6 (R)-Catalyst 4a (n=2): Yield: 60%. Mp (open capillary) 'C (dec), IR: (Film, THF complex) 2951, 2867, 2054, 1754, 1620, 1544, 1533; MS (electrospray) caled for [C 68 H 9 0 Cr 2 N OH]+ = 1211, found (R)-Catalyst 4b (n=4): Yield: 57%. Mp (open capillary) 'C (dec), IR: (Film, THF complex) 2950, 2867, 2055, 1754, 1621, 1547, 1532; MS (electrospray) calcd for [C 70 H 94 Cr 2 N OH]+ = 1239, found 123 (R)-Catalyst 4c (n=5): Yield: 52%. Mp (open capillary) oc (dec), IR: (Film, THF complex) 2950, 2865, 2055, 1751, 1619, 1544, 1533; MS (electrospray) calcd for [C 7 lh 96 Cr 2 N OH]+ = 1253, found (R)-Catalyst 4d (n=6): Yield: 72%. Mp (open capillary) C (dec), IR: (Film, THF complex) 2950, 2866, 2055, 1751, 1621, 1544, 1533; MS (electrospray) calcd for [C 72 H 98 Cr 2 N OH]+ = 1267, found (S)-Catalyst 4d (n=6): Yield: 68%. Mp (open capillary) oc (dec), IR: (Film, THF complex) 2950, 2867, 2055, 1752, 1620, 1544, 1533; MS (electrospray) calcd for [C 72 H 98 Cr 2 N OH]' = 1267, found (R)-Catalyst 4e (n=7): Yield: 51%. Mp (open capillary) 'C (dec), IR: (Film, THF complex) 2950, 2866, 2055, 1750, 1621, 1542; MS (electrospray) calcd for [C 73 HlooCr 2 N 4 0s +OH]+ = 1281, found (R)-Catalyst 4f (n=8): Yield: 48%. Mp (open capillary) oc (dec), IR: (Film, THF complex) 2950, 2865, 2055, 1750, 1621, 1542; MS (electrospray) calcd for [C 7 4 H 10 2 Cr 2 N 4 0s +OH]+ = 1295, found (R)-Catalyst 4g (n=10): Yield: 71%. Mp (open capillary) 'C (dec), IR: (Film, THF complex) 2950, 2865, 2055, 1752, 1621, 1546, 1533; MS (electrospray) calcd for [C 7 6 H10 6 Cr 2 N 4 0s +OH]+ = 1323, found (R)-Acetate Monomer 5: Yield: 75%. Mp (open capillary) oc (dec), IR: (film, THF complex) 2951, 2867, 2055, 1751, 1622, 1546, 1532; MS (FAB) calcd for [C 34 H 46 CrN ] = , found General Procedure for the Kinetic Measurements: Catalyst (0.12 mmol) was dissolved in cyclopentene oxide (2.00 ml, 22.9 mmol) and stirred for 6 h. An aliquot of this catalyst solution was added to a mixture of cyclopentene oxide and 1.00 ml hydrazoic acid (1.50 M) in ether such that [HN 3 ]0 = 1.00 M and [cyclopentene oxide]o = 3.82 M for each run. Formation of product was observed by monitoring growth of the characteristic alkyl azide peak of the product at 2104 cm 1 using an ASI 1000 React-IR probe. The initial rate of product formation was determined from the slope of the line fit to abs vs. time for the data collected during the first 33% of the reaction. A representative run is provided below in Figure S-1, and the numerical data used for the plots in Figure 1 of the main text are listed below in Table S-1. Independent analysis of the rate of product formation measured by monitoring growth of a product peak at 1243 cm- provided quantitatively similar values for kobs (± <5%). S-6

8 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page Figure S-1: Representative Data From Kinetics Measurements [Catalyst 4c (n=5)] = M y = e-4x e-3 R Time (minutes) Table S-1: Numerical Data for Plots in Figure 1 1 (Monomer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-) E E E E E E E E E E E E-03 5 (Acetate Monomer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-') E E E E E E E E E E E E-03 4a (n=2 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min') E E E E E E E E E E E E-02 S-7

9 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page 8 4b (n=4 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min E E E E E E E E E E E E E E E-02 4c (n=5 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-') E E E E OE E E-04 6.OOE E E E E E E E E E E-01 4d (n=6 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-) E E E E E E E E E E E E E E E-01 4e (n=7 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min- ) E E E E E E E E E E E E E E E-01 4f (n=8 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-') E E E E E E E E E E E E-01 S-8

10 1998 American Chemical Society, J. Am. Chem. Soc., Konsler ja982683c Supporting Info Page 9 4g (n=10 dimer) [catalyst] M kobs (absorbance/min) kobs (M product/min) kobs/[cat] (min-) E E E E E E E E E E E E E E E-02 Non-linear Effect Studies: Catalyst [(SS),(SS)]-4d (6.6 mg, 4.9 x 10-6 M) was dissolved in a solution of cyclopentene oxide (5.00 M) in tert-butyl methyl ether (1.OOmL) and stirred for 10 h. An identical tert-butyl methyl ether solution of [(R,R),(R,R)]-4d (6.6 mg, 4.9 x 10-6 M) and cyclopentene oxide (5.00 M) was prepared and stirred for 10 h. Relative concentrations of the catalysts were confirmed by diluting aliquots (20 AL x 3) with THF (50 ml) and measuring the characteristic UV absorbance at 265 nm. Reactions were carried out by combining the solutions of the enantiomeric catalysts in the appropriate ratios and then adding a solution of hydrazoic acid solution in ether (1.50 M) such that [cyclopentene oxide]o = 1.0 M, [hydrazoic acid]o = 1.2 M, and [catalyst] = M. All reactions reached completion within 12 h, and the enantiomeric excess of the ring-opened product was determined by GC chromatography as described above. The numerical data used for the plots in Figure 4 of the main text are listed below in Table S- 2. Table S2: Numerical Data for Figure 4 [5] = 0.02 M catalyst ee [product ee [4d] = 0.01 M catalyst ee product ee [4d] = M catalyst ee I product ee I Notes and References (1) Audrieth, L. F.; Gibbs, C. F. Inorg. Synth. 1939, 1, 77. (2) Reddy, D. R.; Thornton, E. R. J. Chem. Soc. Chem. Com. 1992, 172. (3) Fifmey, N. S.; Pospisil, P. J.; Chang, S.; Palucki, M.; Konsler, R. G.; Hansen, K. B.; Jacobsen, E. N. Angew. Chem. Int. Ed. Engl. 1997, 36, S-9