Direct catalytic asymmetric Michael reaction of hydroxyketones: Asymmetric Zn catalysis with a Et2Zn/ linked-BINOL complex

Journal of the American Chemical Society

Volumn 125, Issue 9, 2003, Pages 2582-2590

  Harada, Shinji ^a   Kumagai, Naoya ^a   Kinoshita, Tomofumi ^a   Matsunaga, Shigeki ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ENANTIOMERS;

ADDITION REACTIONS; CATALYSIS; CATALYSTS; SUBSTITUTION REACTIONS;

KETONES;

ACETOPHENONE DERIVATIVE; ALCOHOL DERIVATIVE; KETOL; KETONE DERIVATIVE; ZINC;

ADDITION REACTION; ARTICLE; CATALYSIS; CATALYST; COMPLEX FORMATION; ENANTIOMER; MICHAEL ADDITION; REACTION ANALYSIS;

EID: 0037420322     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028928+     Document Type: Article

References (92)

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9. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
10. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
11. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
12. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
13. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
14. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
15. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
16. Unmodified ketones as donors: (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki, M. Am. Chem. Soc. 1999, 121, 4168. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569. (e) Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669. Unmodified α-hydroxyketones as donors: (f) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (g) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539. (h) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556.
17. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
18. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
19. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
20. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
21. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
22. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
23. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
24. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
25. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
26. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
27. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
28. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
29. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
30. Unmodified ketones as donors: (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395. (b) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573. (d) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. (e) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. (f) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. (g) Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459. For a partially successful attempt, see: (h) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391. Unmodified α-hydroxyketones as donors: (i) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (j) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. See also ref 4d. Unmodified aldehydes as donors: (k) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301. (l) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002. 124, 6798. (m) Bøgevig, A.; Kumaragurubaran, N; Jørgensen, K. A. Chem. Commun. 2002, 620. For highly selective direct aldol reaction using chiral auxiliary: (n) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392.
31. (a) Yamasaki, S.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1999, 40, 307.
32. (b) Yamasaki, S.; Iida, T.; Shibasaki, M. Tetrahedron 1999, 55, 8857
33. (a) List, B. J. Am. Chem. Soc. 2000, 122, 9336.
34. (b) Notz, W.; Sakthivel, K.; Bui, T.; Zhong, G.; Barbas, C. F., III. Tetrahedron Lett. 2001, 42, 199.
35. (c) Juhl, K.; Gathergood, N.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40, 2995.
36. (d) List, B.; Pojarliev, P.; Biller, W. T.; Martin, H. J. J. Am. Chem. Soc. 2002, 124, 827.
37. (e) Córdova, A.; Notz, W.; Zhong, G.; Betancort, J. M.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1842.
38. (f) Córdova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Zhong, G.; Betancort, J. M.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1866.
39. For other promising atom economic asymmetric catalysis for carbon-carbon bond-forming reaction, see alkynylation: (a) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687. For other selected examples of atom economic asymmetric catalysis, see β-lactam synthesis: (b) Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J., III; Lectka, T. J. Am. Chem. Soc. 2000, 122, 7831. (c) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578. α-amination: (d) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254 and references therein. (e) List, B. J. Am. Chem. Soc. 2002, 124, 5656.
40. For other promising atom economic asymmetric catalysis for carbon-carbon bond-forming reaction, see alkynylation: (a) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687. For other selected examples of atom economic asymmetric catalysis, see β-lactam synthesis: (b) Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J., III; Lectka, T. J. Am. Chem. Soc. 2000, 122, 7831. (c) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578. α-amination: (d) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254 and references therein. (e) List, B. J. Am. Chem. Soc. 2002, 124, 5656.
41. For other promising atom economic asymmetric catalysis for carbon-carbon bond-forming reaction, see alkynylation: (a) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687. For other selected examples of atom economic asymmetric catalysis, see β-lactam synthesis: (b) Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J., III; Lectka, T. J. Am. Chem. Soc. 2000, 122, 7831. (c) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578. α-amination: (d) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254 and references therein. (e) List, B. J. Am. Chem. Soc. 2002, 124, 5656.
42. For other promising atom economic asymmetric catalysis for carbon-carbon bond-forming reaction, see alkynylation: (a) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687. For other selected examples of atom economic asymmetric catalysis, see β-lactam synthesis: (b) Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J., III; Lectka, T. J. Am. Chem. Soc. 2000, 122, 7831. (c) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578. α-amination: (d) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254 and references therein. (e) List, B. J. Am. Chem. Soc. 2002, 124, 5656.
43. For other promising atom economic asymmetric catalysis for carbon-carbon bond-forming reaction, see alkynylation: (a) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687. For other selected examples of atom economic asymmetric catalysis, see β-lactam synthesis: (b) Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J., III; Lectka, T. J. Am. Chem. Soc. 2000, 122, 7831. (c) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578. α-amination: (d) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254 and references therein. (e) List, B. J. Am. Chem. Soc. 2002, 124, 5656.
44. For recent reviews on the catalytic asymmetric 1,4-addition reactions, see: (a) Krause, N.; Hoffmann-Röder, A. Synthesis 2001, 171. (b) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 31.
45. For recent reviews on the catalytic asymmetric 1,4-addition reactions, see: (a) Krause, N.; Hoffmann-Röder, A. Synthesis 2001, 171. (b) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 31.
46. For recent leading references, see: Yamaguchi, M.; Shiraishi, T.; Hirama, M. J. Org. Chem. 1996, 61, 3520. See also ref 17a.
47. For recent leading references, see: (a) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215.
48. (b) Hamashima, Y.; Hotta, D.; Sodeoka, M. J. Am. Chem. Soc. 2002, 124, 11240 and references therein. See also:
49. (c) Sawamura, M.; Hamashima, H.; Ito, Y. Tetrahedron 1994, 50, 4439 for α-cyano esters.
50. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
51. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
52. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
53. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
54. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
55. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
56. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
57. Excellent catalytic asymmetric 1,4-addition reactions with latent enolates, such as enol silyl ether, are established (>90% ee), although those reactions require stoichiometric amounts of reagents to prepare latent enolates. For recent representative examples, see: (a) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem Lett. 1994, 97. (b) Kitajima, H.; Ito, K.; Katsuki, T. Tetrahedron 1997, 53, 17015. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134. (d) Zhang, F.-Y.; Corey, E. J. Org. Lett. 2001, 3, 639. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. J. Am. Chem. Soc. 200, 123, 4480 and references therein. For leading references on catalytic asymmetric 1,4-addition reactions of other carbon nucleophiles, see Zn reagents: (f) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. B reagents: (g) Hayashi, T. Synlett 2001, 879. Ti reagents: (h) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J.-W. J. Am. Chem. Soc. 2002, 124, 12102.
58. Zhang, F.-Y.; Corey, E. J. Org. Lett. 2000, 2, 1097.
59. (a) Betancort, J. M.; Sakthivel, K.; Thayumanavan, R.; Barbas, C. F., III. Tetrahedron Lett. 2001, 42, 4441.
60. (b) List, B.; Pojarliev, P.; Martin, H. J. Org. Lett. 2001, 3, 2423. Unmodified aldehydes as donors:
61. (c) Betancort, J. M.; Barbas, C. F., III. Org. Lett. 2001, 3, 3737.
62. (d) Enders, D.; Seki, A. Synlett 2002, 26.
63. (e) Alexakis, A.; Andrey, O. Org. Lett. 2002, 4, 3611.
64. Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251.
65. For the synthesis and application of linked-BINOL, see: (a) Matsunaga, S.; Das, J.; Roels, J.; Vogl, E. M.; Yamamoto, N.; Iida, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 2252. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Adv. Synth. Catal. 2002, 344, 4. Linked-BINOL is also commercially available from Wako Pure Chemical Industries, Ltd. Catalog No. 152-02431 for (S,S)-ligand, No. 155-02421 for (R,R)-ligand. Fax +1-804-271-7791 (USA), +81-6-6201-5964 (Japan), +81-3-5201-6590 (Japan).
66. For the synthesis and application of linked-BINOL, see: (a) Matsunaga, S.; Das, J.; Roels, J.; Vogl, E. M.; Yamamoto, N.; Iida, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 2252. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Adv. Synth. Catal. 2002, 344, 4. Linked-BINOL is also commercially available from Wako Pure Chemical Industries, Ltd. Catalog No. 152-02431 for (S,S)-ligand, No. 155-02421 for (R,R)-ligand. Fax +1-804-271-7791 (USA), +81-6-6201-5964 (Japan), +81-3-5201-6590 (Japan).
67. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. See also refs 4f and 4g. For related compounds: (d) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (e) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
68. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. See also refs 4f and 4g. For related compounds: (d) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (e) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
69. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. See also refs 4f and 4g. For related compounds: (d) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (e) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
70. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. See also refs 4f and 4g. For related compounds: (d) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (e) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
71. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. See also refs 4f and 4g. For related compounds: (d) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (e) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
72. 2-Zn/linked-BINOL Complex (1) by Kumagai, N.; Matsunaga, S.; Kinoshita, T.; Harada, S.; Okada, S.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M., See, also refs 4f and 4g.
73. The relative configurations of 6a, 8g, and 8o were determined by X-ray analysis, see Supporting Information. The absolute configurations of the carbinolic stereocenters on 4c, 6a, and 8i were determined by Mosher's method. Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512.
74. For the beneficial effects of additional achiral base to enhance the reaction rate of bifunctional asymmetric catalysis: (a) Arai, T.; Yamada, Y. M. A.; Yamamoto, N.; Sasai, H.; Shibasaki, M. Chem.-Eur. J. 1996, 2, 1368. (b) Tian, J.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2002, 41, 3636.
75. For the beneficial effects of additional achiral base to enhance the reaction rate of bifunctional asymmetric catalysis: (a) Arai, T.; Yamada, Y. M. A.; Yamamoto, N.; Sasai, H.; Shibasaki, M. Chem.-Eur. J. 1996, 2, 1368. (b) Tian, J.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2002, 41, 3636.
76. Review: Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388.
77. For excellent achievements in catalytic asymmetric hydrogenation of ketones, see review: Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40 and references therein.
78. Tamura, Y.; Fujiwara, H.; Sumoto, K.; Ikeda, M.; Kita, Y. Synthesis 1973, 215.
79. (a) Porter, J. R.; Traverse, J. F.; Hoveyda, A. H.; Snapper, M. C. J. Am. Chem. Soc. 2001, 123, 10409.
80. (b) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180 and references therein.
81. Tanga, M. J.; Reist, E. J. J. Heterocycl. Chem. 1986, 23, 747.
82. 2 9 -9 major + aldol adduct recovery and reuse(three times)
83. In the direct aldol reaction of 3 with Zn/linked-BINOL complex, the maximum substrate/chiral ligand ratio was 1000, probably due to the product (dihydroxyketone) inhibition.
84. See Supporting Information for detailed results, including numerical data.
85. For precedent examples where activated molecular sieves had a key role to accelerate the product dissociation step in the catalytic cycle, see: Iida, T.; Yamamoto, N.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc. 1997, 119, 4783 and references therein.
86. 18
87. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
88. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
89. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
90. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
91. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
92. Bifunctional mechanism was proposed for the reaction by achiral dinuclear Zn complexes as zinc metalloenzyme models. For selected recent examples, see: (a) Chapman, W. H., Jr.; Breslow, R. J. Am. Chem. Soc. 1995, 117, 5462. (b) Yashiro, M.; Ishikubo, A.; Komiyama, M. J. Chem. Soc., Chem. Commun. 1995, 1793. (c) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (d) Molenveld, P.; Kapsabeils, S.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Am. Chem. Soc. 1997, 119, 2948. (e) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (f) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.