Highly enantioselective conjugate additions to α,β-unsaturated ketones catalyzed by a (salen)Al complex

Journal of the American Chemical Society

Volumn 127, Issue 4, 2005, Pages 1313-1317

  Taylor, Mark S ^a   Zalatan, David N ^a   Lerchner, Andreas M ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; MOLECULAR STRUCTURE; STEREOCHEMISTRY; UNSATURATED COMPOUNDS;

CHIRAL BUILDING BLOCKS; HETEROCYCLIC COMPOUNDS; SYNTHETIC MANIPULATIONS; UNSATURATED KETONES;

KETONES;

ALUMINUM DERIVATIVE; CARBON; HETEROCYCLIC COMPOUND; KETONE; NITRILE; NITROGEN;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; CONJUGATE; ENANTIOSELECTIVITY; METHODOLOGY; SYNTHESIS;

ALKANES; ALUMINUM; AZIDES; CATALYSIS; ETHYLENEDIAMINES; KETONES; NITRILES; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM;

EID: 13644249902     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja044999s     Document Type: Article

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14. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
15. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
16. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
17. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
18. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
19. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
20. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
21. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
22. For conjugate addition of β-dicarbonyl compounds to cyclic enones, see: (a) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571-1572. (b) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198. (c) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106. (d) Majima. K.; Takita, R.; Okada, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837-15845. For hydroperoxide epoxidation of enones and acid imidazolides, see: (e) Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725-2732 and references therein, (f) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474-9475. For conjugate addition of nitroalkanes to chalcones, see: (g) Funabashi, K.; Saida, Y.; Kanai, M.; Sasai, H.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7557-7558. For conjugate addition of O-alkylhydroxylamines to enones, see: (h) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178-16179. For conjugate additions to N-acylpyrroles, see: (i) Kinoshita, T.; Okada, S.; Park, S.-R.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2003, 42, 4680-4684. (j) Natsunaga, S.; Kinoshita, T.; Okada, S.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559-7570.
23. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
24. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
25. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
26. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
27. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
28. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
29. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
30. For the Mukaiyama Michael reaction, see: (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335 and references therein. For conjugate addition of electron-rich aryl groups, see: (b) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40. 160-163. (c) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002, 124, 9030-9031. (d) Evans, D. A.; Scheidt, K. A.; Fandrick, K. R.; Lam, H. W.; Wu, J. J. Am. Chem. Soc. 2003, 125, 10780-10781. For conjugate addition of carbamates, see: (e) Palumo. C.; Oiarbide, M.; Halder, R.; Kelso, M.; Gómez-Bengoa, E.; García, J. M. J. Am. Chem. Soc. 2004, 126, 9188-9189. (f) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (g) Sibi, M. P.; Liu, M. Org. Lett. 2000, 2, 3393-3396. (h) Sibi, M. P.; Prabagaran, N.; Ghorpade, S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, 11796-11797.
31. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
32. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
33. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
34. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
35. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
36. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
37. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
38. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
39. For conjugate addition of β-dicarbonyl compounds, see: (a) Yamaguchi, M.; Shiraishi, T.; Hirama, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1173-1175. (b) Halland, N.; Aburel, P. S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 661-665. (c) Halland, N.; Hansen, T.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2003, 42, 4955-4957. For conjugate addition of nitroalkanes, see: (d) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978. (e) Halland, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 8331-8338. For conjugate addition of electron-rich aryl groups, see: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371. (g) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173. (h) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895. For the Mukaiyama Michael reaction, see: (i) Brown, S. P.; Goodwin, N. C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125, 1192-1194.
40. (a) Myers, J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-5960.
41. (b) Sammis, G. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2003, 125, 4442-4443.
42. (c) Taylor, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 2003, 125, 11204-11205.
43. (d) Vanderwal, C. D.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 14724-14725.
44. (e) Chen, Q.; Delmonte, A. G.; Gandelman, M. A.; Jacobsen, E. N. Unpublished results.
45. (a) Salen-Red-Al-catalyzed Michael additions to cyclic ketones have been described: Jha, S. C.; Joshi, N. N. Tetrahedron: Asymmetry 2001, 12, 2463-2466.
46. (b) Catalyst 1c has been employed in enantioselective conjugate additions of indoles to 1-aryl-3-buten-2-ones: Bandini, M.; Fagioli, M.; Melchiorre, P.; Melloni, A.; Umani-Ronchi, A. Tetrahedron Lett. 2003, 44, 5843-5846.
47. For a review, see: Yamaguchi, M. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 3, Chapter 31.2.
48. (Salen)aluminum complexes 1a-c (10 mol % Al loading) were tested as catalysts for the addition of methyl cyanoacetate to 4-phenyl-3-buten-2-one (0.2 M cyclohexane, 23°C, 6.5 h). 1a: 93% conversion, 94% ee. 1b: 61% conversion, 94% ee. 1c: <2% conversion.
49. Various solvents were tested for the addition of methyl cyanoacetate to 4-phenyl-3-buten-2-one (5 mol % 1a, 0.2 M solvent, 23°C, 14 h). In general, highest yields and enantioselectivities were observed in solvents having low dielectric constants. Diethyl ether: 96% conversion, 90% ee. Toluene: 97% conversion, 89% ee. Tetrahydrofuran: 87% conversion, 88% ee. Dichloromethane: 60% conversion, 62% ee.
50. High (>90%) enantioselectivities for this transformation have been limited to chalcone derivatives and cyclic substrates. See refs 6g and 8d and: Bakó, P.; Bojor, Z.; Töke, L. J. J. Chem. Soc., Perkin Trans. 1 1999, 3651-3655. Jørgensen and co-workers (ref 8e) have reported conjugate additions of nitroalkanes to α,α-unsaturated methyl ketones, providing the products in 50-99% yield and 49-86% ee.
51. Enones bearing β-alkyl substituents were found to undergo moderately enantioselective conjugate additions, but poor yields were obtained due to slow reaction rates. For example, addition of nitromethane to 3-hexen-2-one proceeded in 75% ee and 31% yield after 72 h using 7.5 mol % 1a.
52. Krapcho, A. P. Synthesis 1982, 805-822 and 893-913.
53. Dwyer, M. P.; Lamar, J. E.; Meyers, A. I. Tetrahedron Lett. 1999, 40, 8965-8968.
54. (a) Carvone, a naturally occurring 5-substituted 3-cyclohexen-1-one, has been used as a starting material for the synthesis of complex natural products. For examples, see: Srikrishna, A.; Satyanarayana, G. Org. Lett. 2004, 6, 3143-3144 and references therein.
55. (b) For a recent example of the application of synthetic 3-cyclohexen-1-ones in natural product synthesis, see: Miyashita, M.; Sasaki, M.; Hattoria, L; Sakai, M.; Tanino, K. Science 2004, 305, 495-499.
56. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
57. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
58. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
59. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
60. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
61. Several diastereoselective approaches to this class of compounds have been developed: (a) Schwarz, J. B.; Devine, P. N.; Meyers, A. I. Tetrahedron 1997, 53, 8795-8806. (b) Schwarz, J. B.; Meyers, A. I. J. Org. Chem. 1998, 63, 1732-1735. (c) Hikichi, S.; Hareau, G. P.-J.; Sato, F. Tetrahedron Lett. 1997, 38, 8299-8302. (d) Sarakinos. G.; Corey, E. J. Org. Lett. 1999, 1, 811-814. (e) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640-3650. (f) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 927-930 (catalytic kinetic resolution approach).
62. See refs 7e-h, 9a, and: Guerin, D. J.; Miller, S. J. J. Am. Chem. Soc. 2002, 124, 2134-2136.
63. For an example of the synthesis of β-amino ketones by asymmetric Mannich reaction, see: List, B. J. Am. Chem. Soc. 2000, 122, 9336-9337.
64. For the in situ generation of hydrazoic acid from azidotrimethylsilane and carboxylic acids, see: Guerin, D. J.; Horstmann, T. E.; Miller, S. J. Org. Lett. 1999, 1, 1107-1109.
65. The conjugate addition of hydrazoic acid to cyclic enones catalyzed by 1a proceeds with low enantioselectivity. 3-Azidocyclohexanone and 3-azidocycloheptanone are obtained in 8 and 14% ee, respectively (5 mol % la, methylcyclohexane, -40°C).
66. The conjugate addition of hydrazoic acid to 4-phenyl-3-buten-2-one proceeds to 14% conversion in 79% ee after 14 h (5 mol % 1a, methylcyclohexane, -45°C).
67. Saito, S.; Nakajima, H.; Inaba, M.; Moriwake, T. Tetrahedron Lett. 1989, 30, 837-838.
68. For a prior demonstration of this approach to enantioenriched triazoles, see ref 20.
69. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2596-2599.
70. The heterogeneity of the reaction mixtures in the enone conjugate addition reactions has limited our ability to carry out accurate kinetic analyses of these processes. However, studies on closely related additions to α,β-unsaturated imides catalyzed by 1a point to a cooperative mechanism wherein the catalyst activates both nucleophile and electrophile. See ref 9e and: Sammis, G. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 9928-9929.