Asymmetric synthesis of pyrrolidinoindolines. Application for the practical total synthesis of (-)-phenserine

Journal of the American Chemical Society

Volumn 126, Issue 43, 2004, Pages 14043-14053

  Huang, Audris ^a   Kodanko, Jeremy J ^a   Overman, Larry E ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYLATION; CHEMICAL ANALYSIS; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

DIALKYLATION; ELECTROPHILE; ENANTIOPURE;

ORGANIC COMPOUNDS;

5 METHOXY 1,3 DIMETHYLOXINDOLE; INDOLE DERIVATIVE; OXINDOLE; PHENSERINE; PHYSOSTIGMINE; PYRROLIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CHEMICAL PROCEDURES; CHEMICAL REACTION; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS; THEORETICAL MODEL;

ALKYLATION; INDOLES; PHYSOSTIGMINE; PYRROLIDINES; STEREOISOMERISM;

EID: 7444242718     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046690e     Document Type: Article

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20. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
21. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
22. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
23. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
24. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
25. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
26. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
27. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
28. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
29. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
30. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
31. For physostigmine, see: (a) Tanaka, K.; Taniguchi, T.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 1049-1052. (b) Kawahara, M.; Nishida, A.; Nakagawa, M. Org. Lett. 2000, 2, 675-678. (c) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500-6503. (d) Node, M.; Hao, X.; Nishide, K.; Fuji, K. Chem. Pharm. Bull. 1996, 44, 715-719. (e) Pei, X.-F.; Yu, Q.-S.; Lu, B.-Y.; Greig, N. H.; Brossi, A. Heterocycles 1996, 42, 229-236. (f) Pallavicini, M.; Valoti, E.; Villa, L.; Resta, I. Tetrahedron: Asymmetry 1994, 5, 363-370. (g) Ashimori, A.; Matsuura, T.; Overman, L. E.; Poon, D. J. J. Org. Chem. 1993, 58, 6949-6951. (h) Marino, J. P.; Bogdan, S.; Kimura, K. J. Am. Chem. Soc. 1992, 114, 5566-5572. (i) Lee, T. B. K.; Wong, G. S. K. J. Org. Chem. 1991, 56, 872-875. (j) Takano, S.; Moriya, M.; Ogasawara, K. J. Org. Chem. 1991, 56, 5982-5984. (k) Node, M.; Itoh, A.; Masaki, Y.; Fuji, K. Heterocycles 1991, 32, 1705-1707. (l) Takano, S.; Sato, T.; Inomata, K.; Ogasawara, K. Heterocycles 1990, 31, 411-414. (m) Takano, S.; Moriya, M.; Iwabuchi, Y.; Ogasawara, K. Chem. Lett. 1990, 109-112.
32. This strategy traces back to the original Julian synthesis of (±)-physostigmine: (a) Julian, P. L.; Pikl, J. J. Am. Chem. Soc. 1935, 57, 563-566. (b) Julian, P. L.; Pikl, J. J. Am. Chem. Soc. 1935, 57, 755-757.
33. This strategy traces back to the original Julian synthesis of (±)-physostigmine: (a) Julian, P. L.; Pikl, J. J. Am. Chem. Soc. 1935, 57, 563-566. (b) Julian, P. L.; Pikl, J. J. Am. Chem. Soc. 1935, 57, 755-757.
34. (a) Pei, X.-F.; Brossi, A. Heterocycles 1995, 41, 2823-2826.
35. (b) Pallavicini, M.; Valoti, E.; Villa, L.; Lianza, F. Tetrahedron: Asymmetry 1994, 5, 111-116.
36. (a) Brossi, A.; Pei, X.-F.; Greig, N. H. Aust. J. Chem. 1996, 49, 171-181.
37. (b) Brzostowska, M.; He, X.-S.; Greig, N. H.; Rapoport, S. I.; Brossi, A. Med. Chem. Res. 1992, 2, 238-246.
38. Kodanko, J. J.; Overman, L. E. Angew. Chem., Int. Ed. 2003, 42, 2528-2531.
39. Kodanko, J. J. Methods for Synthesis of the High Order Polypyrrolidinoindolines and Total Synthesis of the Hodgkinsine Trispyrrolidinoindolines; Ph.D. Dissertation, University of California, Irvine, CA, 2003.
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41. (a) Overman, L. E.; Larrow, J. F.; Stearns, B. A.; Vance, J. M. Angew. Chem., Int. Ed. 2000, 39, 213-215.
42. (b) Hoyt, S. B.; Overman, L. E. Org. Lett. 2000, 2, 3241-3244.
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44. Villemin, D.; Martin, B. Synth. Commun. 1998, 28, 3201-3208.
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52. (a) An-naka, M.; Yasuda, K.; Yamada, M.; Kawai, A.; Takamura, N.; Sugasawa, S.; Matsuoka, Y.; Iwata, H.; Fukushima, T. Heterocycles 1994, 39, 251-270.
53. (b) Gassman, P. G.; van Bergen, T. J. J. Am. Chem. Soc. 1974, 96, 5508-5512.
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55. Paquette, L. A.; Farkas, E.; Galemmo, R. J. Org. Chem. 1981, 46, 5434-5436.
56. Reddy, S. H. K.; Chiba, K.; Sun, Y.; Moeller, K. D. Tetrahedron 2001, 57, 5183-5197.
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59. Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6488-6499.
60. (a) Kraus, G. A.; Taschner, M. J. J. Org. Chem. 1980, 45, 1175-1176.
61. (b) Lindgren, B. O.; Nilsson, T. Acta Chem. Scand. 1973, 27, 888-890.
62. (a) Lebsack, A. D.; Link, J. T.; Overman, L. E.; Stearns, B. A. J. Am. Chem. Soc. 2002, 124, 9008-9009.
63. (b) Iwao, M.; Kuraishi, T. Org. Synth. 1996, 73, 85-93.
64. Absolute configuration was assigned by analysis of the anomalous dispersion using Rogers's η parameter: Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876-881.
65. Haddach, A. A.; Kelleman, A.; Deaton-Rewolinski, M. V. Tetrahedron Lett. 2002, 43, 399-402.
66. The quaternary stereocenters of 30a and 31a were assigned the R absolute configurations by analogy to the relative and absolute configurations established for compounds 28a, 29a, and 32a-36a.
67. 13C NMR of 63.
68. 2) using either NaHMDS, LHMDS, or KHMDS as the base.
69. Yu, Q.-S.; Brossi, A. Heterocycles 1988, 27, 745-750.
70. Brossi, A.; Brzostowska, M.; Rapoport, S.; Greig, N.; He, X. S. Substituted phenserines and phenylcarbamates of (-)-eseroline, (-)-N1-noreseroline, and (-)-N1-benzylnoreseroline; as specific inhibitors of acetylcholinesterase. WO 9306105 A1, April 1, 1993.
71. For recent reviews of asymmetric synthesis of quaternary carbon centers, see: (a) Douglas, C. J.; Overman, L. E. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5363-5367. (b) Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388-401. (c) Fuji, K. Chem. Rev. 1993, 93, 2037-2066.
72. For recent reviews of asymmetric synthesis of quaternary carbon centers, see: (a) Douglas, C. J.; Overman, L. E. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5363-5367. (b) Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388-401. (c) Fuji, K. Chem. Rev. 1993, 93, 2037-2066.
73. For recent reviews of asymmetric synthesis of quaternary carbon centers, see: (a) Douglas, C. J.; Overman, L. E. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5363-5367. (b) Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388-401. (c) Fuji, K. Chem. Rev. 1993, 93, 2037-2066.
74. (a) A recent survey of stereoselective C-C bond-formation cites no examples of alkylation reactions with chiral electrophiles: Methoden Org. Chem. (Houben-Weyl), 4th Ed., 1996; Vol. E21-E22, pp 1077-1118 (Workbook Edition).
75. (b) For examples of selectivity in the range of 7-10:1 in alkylations of lactate Inflates, see: Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813-5814.
76. N2 transition structure would be favored also by this stereoelectronic feature.
77. Streitwieser, A. Solvolytic Displacement Reactions; McGraw-Hill: New York, 1962; pp 16-20.
78. The erosion of stereoselection observed in the reaction of the lithium enolate of oxindole 27 with ditriflate 10 as the DMPU content of the solvent is increased from 2 to 30% (Table 2) would be consistent with the importance of electrostatic or dipole interactions in organizing the alkylation transition state.
79. 2-symmetric isomer.
80. It is not surprising that this substituent would effect diastereoselection in the initial alkylation step and the oxindolemethyl substituent in the second. Interactions of these groups with the triflate leaving group could modulate the alignment of the C1-C2 σ-bond of the electrophile and/or the conformation of the dioxolane ring, with the latter orienting the dimethyl group in a way that influences the approach of the nucleophile.
81. General experimental details have been described: Ando, S.; Minor, K. P.; Overman, L. E. J. Org. Chem. 1997, 62, 6379-6387.
82. Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as a supplementary publication: CCDC-241957 (61) and CCDC-241958 (62).