Enantioselective Synthesis of (-)-Pumiliotoxin C from a Chiral Amino Ester and an Acetylenic Sulfone that Acts as an Alkene Dipole Equivalent

Journal of Organic Chemistry

Volumn 63, Issue 19, 1998, Pages 6566-6571

  Back, Thomas G ^a   Katsumasa, Nakajima ^a  

^a UNIVERSITY OF CALGARY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001680511     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980647q     Document Type: Article

References (83)

1. For reviews, see: (a) Witkop, B.; Gössinger, E. In The Alkaloids: Chemistry and Pharmacology; Brossi, A., Ed.; Academic Science: New York, 1983; Vol. 21, Chapter 5. (b) Daly, J. W.; Spande, T. F. Alkaloids: Chemical and Biological Perspectives; Pelletier, S. W., Ed.; Wiley-Interscience: New York, 1986; Vol. 4, pp 1-274.
2. For reviews, see: (a) Witkop, B.; Gössinger, E. In The Alkaloids: Chemistry and Pharmacology; Brossi, A., Ed.; Academic Science: New York, 1983; Vol. 21, Chapter 5. (b) Daly, J. W.; Spande, T. F. Alkaloids: Chemical and Biological Perspectives; Pelletier, S. W., Ed.; Wiley-Interscience: New York, 1986; Vol. 4, pp 1-274.
3. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
4. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
5. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
6. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
7. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
8. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
9. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
10. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
11. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
12. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
13. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
14. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
15. For lead references, see: (a) Daly, J. W.; Brown, G. B.; Mensah-Dwumah, M.; Myers, C. W. Toxicon 1978, 16, 163. (b) Mensah-Dwumah, M.; Daly, J. W. Toxicon 1978, 16, 189. (c) Daly, J. W.; Myers, C. W.; Whittaker, N. Toxicon 1987, 25, 1023. (d) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Cover, J. F., Jr. Toxicon 1994, 32, 657. (e) Tokuyama, T.; Tsujita, T.; Shimada, A.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron 1991, 47, 5401. (f) Daly, J. W.; Secunda, S. I.; Garraffo, H. M.; Spande, T. F.; Wisnieski, A.; Nishihira, C.; Cover, J. F., Jr. Toxicon 1992, 30, 887. (g) Tokuyama, T.; Nishimori, N.; Shimada, A.; Edwards, M. W.; Daly, J. W. Tetrahedron 1987, 43, 643. (h) Daly, J. W.; Witkop, B.; Tokuyama, T.; Nishikawa, T.; Karle, I. L. Helv. Chim. Acta 1977, 60, 1128. (i) Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly, J. W. Tetrahedron 1986, 42, 3453. (j) Edwards, M. W.; Daly, J. W.; Myers, C. W. J. Nat. Prod. 1988, 51, 1188. (k) Daly, J. W.; Highet, R. J.; Myers, C. W. Toxicon 1984, 22, 905, (l) Garraffo, H. M.; Caceres, J.; Daly, J. W.; Spande, T. F.; Andriamaharavo, N. R.; Andriantsiferana, M. J. Nat. Prod. 1993, 56, 1016. (m) Daly, J. W.; Garraffo, H. M.; Pannell, L. K.; Spande, T. F. J. Nat. Prod. 1990, 53, 407.
16. Daly, J. W.; Tokuyama, T.; Habermehl, G.; Karle, I. L., Witkop, B. Liebigs Ann. Chem. 1969, 729, 198.
17. (a) Warnick, J. E.; Jessup, P. J.; Overman, L. E.; Eldefrawi, M. E.; Nimit, Y.; Daly, J. W.; Albuquerque, E. X. Mol. Pharmacol. 1982, 22, 565.
18. (b) Daly, J. W.; Nishizawa, Y.; Padgett, W. L.; Tokuyama, T.; McCloskey, P. J.; Waykole, L.; Schultz, A. G.; Aronstam, R. S. Neurochem. Res. 1991, 16, 1207.
19. (a) Kuethe, J. T.; Padwa, A. Tetrahedron Lett. 1997, 38, 1505.
20. (b) Mehta, G.; Praveen, M. J. Org. Chem. 1995, 60, 279.
21. (c) Meyers, A. I.; Milot, G. J. Am. Chem. Soc. 1993, 115, 6652.
22. (d) Polniaszek, R. P.; Dillard, L. W. J. Org. Chem. 1992, 57, 4103.
23. (e) Brandi, A.; Cordero, F. M.; Goti, A.; Guarna, A. Tetrahedron Lett. 1992, 33, 6697.
24. (f) Comins, D. L.; Dehghani, A. Tetrahedron Lett. 1991, 32, 5697.
25. (g) LeBel, N. A.; Balasubramanian, N. J. Am. Chem. Soc. 1989, 111, 3363.
26. (h) Abe, K.; Tsugoshi, T.; Nakamura, N. Bull. Chem. Soc. Jpn. 1984, 57, 3351.
27. (i) Maruoka, K.; Miyazaki, T.; Ando, M.; Matsumura, Y.; Sakane, S.; Hattori, K.; Yamamoto, H. J. Am. Chem. Soc. 1983, 105, 2831.
28. (j) Overman, L. E.; Jessup, P. J. J. Am. Chem. Soc. 1978, 100, 5179.
29. (k) Ibuka, T.; Mori, Y.; Inubushi, Y. Chem. Pharm. Bull. 1978, 26, 2442.
30. (l) Oppolzer, W.; Fehr, C.; Warneke, J. Helv. Chim. Acta 1977, 60, 48.
31. (m) Habermehl, G.; Andres, H.; Miyahara, K.; Witkop, B.; Daly, J. W. Liebigs Ann. Chem. 1976, 1577.
32. (n) Oppolzer, W.; Fröstl, W.; Weber, H. P. Helv. Chim. Acta 1975, 58, 593.
33. (o) Ibuka, T.; Masaki, N.; Saji, I.; Tanaka, K.; Inubushi, Y. Chem. Pharm. Bull. 1975, 23, 2779.
34. (a) Naruse, M.; Aoyagi, S.; Kibayashi, C. J. Chem. Soc., Perkin Trans. 1 1996, 1113.
35. (b) Comins, D. L.; Dehghani, A. J. Chem. Soc., Chem. Commun. 1993, 1838.
36. (c) Murahashi, S.; Sasao, S.-I.; Saito, E.; Naota, T. Tetrahedron 1993, 49, 8805.
37. (d) Bonin, M.; Royer, J.; Grierson, D. S.; Husson, H.-P. Tetrahedron Lett. 1986, 27, 1569.
38. (e) Oppolzer, W.; Flaskamp, E. Helv. Chim. Acta 1977, 60, 204.
39. (a) Toyota, M.; Asoh, T.; Matsuura, M.; Fukumoto, K. J. Org. Chem. 1996, 61, 8687.
40. (b) Toyota, M.; Asoh, T.; Fukumoto, K. Tetrahedron Lett. 1996, 37, 4401.
41. (c) Schultz, A. G.; McCloskey, P. J.; Court, J. J. J. Am. Chem. Soc. 1987, 109, 6493.
42. (d) Masamune, S.; Reed, L. A., III. Davis, J. T.; Choy, W. J. Org. Chem. 1983, 48, 4441.
43. Preliminary communication of the synthesis of racemic 1: Back, T. G.; Nakajima, K. Tetrahedron Lett. 1997, 38, 989.
44. For reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Trost, B. M. Bull. Chem. Soc. Jpn. 1988, 61, 107. (d) Simpkins, N. S. Tetrahedron 1990, 46, 6951. (e) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; Wiley: Chichester, 1988; Chapter 15.
45. For reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Trost, B. M. Bull. Chem. Soc. Jpn. 1988, 61, 107. (d) Simpkins, N. S. Tetrahedron 1990, 46, 6951. (e) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; Wiley: Chichester, 1988; Chapter 15.
46. For reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Trost, B. M. Bull. Chem. Soc. Jpn. 1988, 61, 107. (d) Simpkins, N. S. Tetrahedron 1990, 46, 6951. (e) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; Wiley: Chichester, 1988; Chapter 15.
47. For reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Trost, B. M. Bull. Chem. Soc. Jpn. 1988, 61, 107. (d) Simpkins, N. S. Tetrahedron 1990, 46, 6951. (e) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; Wiley: Chichester, 1988; Chapter 15.
48. For reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Trost, B. M. Bull. Chem. Soc. Jpn. 1988, 61, 107. (d) Simpkins, N. S. Tetrahedron 1990, 46, 6951. (e) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; Wiley: Chichester, 1988; Chapter 15.
49. Back, T. G.; Wehrli, D. Tetrahedron Lett. 1995, 36, 4737.
50. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
51. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
52. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
53. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
54. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
55. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
56. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
57. For examples of conjugate additions of amines to other acetylenic sulfones, see: (a) Truce, W. E.; Brady, D. G. J. Org. Chem. 1966, 31, 3543. (b) Truce, W. E.; Markley, L. D. J. Org. Chem. 1970, 35, 3275. (c) Truce, W. E.; Onken, D. W. J. Org. Chem. 1975, 40, 3200. (d) Stirling, C. J. M. J. Chem. Soc. 1964, 5863. (e) Pink, R. C.; Spratt, R.; Stirling, C. J. M. J. Chem. Soc. 1965, 5714. (f) McMullen, C. H.; Stirling, C. J. M. J. Chem. Soc. B 1966, 1217. (g) McDowell, S. T.; Stirling, C. J. M. J. Chem. Soc. B 1967, 351. (h) Cossu, S.; De Lucchi, O.; Durr, R. Synth. Commun. 1996, 26, 4597.
58. For examples of reactions of other enamine sulfones with electrophiles, see: (a) Back, T. G.; Collins, S.; Law, K.-W. Can. J. Chem. 1985, 63, 2313. (b) Fatutta, S.; Pitacco, G.; Russo, C.; Valentin, E. J. Chem. Soc., Perkin Trans, 1 1982, 2045.
59. For examples of reactions of other enamine sulfones with electrophiles, see: (a) Back, T. G.; Collins, S.; Law, K.-W. Can. J. Chem. 1985, 63, 2313. (b) Fatutta, S.; Pitacco, G.; Russo, C.; Valentin, E. J. Chem. Soc., Perkin Trans, 1 1982, 2045.
60. Davies, S. G.; Bhalay, G. Tetrahedron: Asymmetry 1996, 7, 1595.
61. Frank, R. L.; Emmick, R. D.; Johnson, R. S. J. Am. Chem. Soc. 1947, 69, 2313.
62. Craig, D. J. Am. Chem. Soc. 1950, 72, 1678.
63. (a) Toone, E. J.; Werth, M. J.; Jones, J. B. J. Am. Chem. Soc. 1990, 112, 4946 and references therein.
64. (b) Ohno, M.; Otsuka, M. Org. React. 1989, 37, 1.
65. (c) Zhu, L.-M.; Tedford, M. C. Tetrahedron 1990, 46, 6587.
66. By analogy to the PLE-mediated hydrolysis of dimethyl cis-1,2-cyclohexanedicarboxylate, and from the active site model described by Jones et al. for the latter compound (ref 16a), we had hoped to obtain 11 directly from (-)-6. Unfortunately, the different behavior of the methyl-substituted cyclohexane diester necessitated the more circuitous approach shown in Scheme 3. A similar switch in the stereoselectivity of hydrolysis of dimethyl cis-1,2-cyclopropanedicarboxylate by PLE was reported when methyl groups were introduced at the 3-position. See: Schneider, M.; Engel, N.; Hönicke, P.; Heinemann, G.; Götisch, H. Angew. Chem., Int. Ed Engl. 1984, 23, 67.
67. Kim, S.; Lee, J. L; Kim, Y. C. J. Org. Chem. 1985, 50, 560.
68. Efforts to separate the mixture of 9 and 10 by chromatography failed. Similarly, conversion of the free carboxylic acid groups of 7 and 8 to their respective esters with methyl mandelate produced inseparable mixtures.
69. GC analysis of (-)-6 obtained in this manner on a chiral column indicated no detectable amount of the (+)-enantiomer under conditions giving a clean separation of the enantiomers of racemic 6 (see the Supporting Information).
70. Shioiri, T.; Ninomiya, K.; Yamada, S. J. Am. Chem. Soc. 1972, 94, 6203.
71. Since the precursor (-)-6 was enantiopure, a very small degree of epimerization apparently occurred during the saponification or Curtius rearrangement steps leading to (-)-3. Enantiopure (-)-3 obtained from recrystallized 13 was again treated with (R)-mandelic acid and subjected to NMR analysis to confirm that further epimerization had not taken place during the basification step.
72. Resolution of racemic 3 via recrystallization of diastereomeric salts produced with mandelic acid proved unsuccessful. For examples of resolutions of other amines with mandelic acid and related compounds, see: Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley-Interscience: New York, 1994; p 334.
73. (a) Back, T. G.; Collins, S.; Kerr, R. G. J. Org. Chem. 1983, 48, 3077.
74. (b) Back, T. G.; Collins, S.; Gokhale, U.; Law, K.-W. J. Org. Chem. 1983, 48, 4776.
75. (c) Miura, T.; Kobayashi, M. J. Chem. Soc., Chem. Commun. 1982, 438.
76. For examples of reductive desulfonylations with Na/Hg, see: ref 9c and references therein.
77. Kobayashi, S.; Kamiyama, K.; Ohno, M. Chem. Pharm. Bull. 1990, 38, 350.
78. Schwartz, N. N.; Blumbergs, J. H. J. Org. Chem. 1964, 29, 1976.
79. Kawasaki, K.; Matsumura, H. Chem. Pharm. Bull. 1969, 17, 1158.
80. Bussert, J. F.; Greenlee, K. W.; Derfer, J. M.; Boord, C. E. J. Am. Chem. Soc. 1956, 78, 6076.
81. Back, T. G.; Collins, S.; Krishna, M. V. Can. J. Chem. 1987, 65, 38.
82. Compound 4 has been previously prepared by a different route: Iwata, N.; Morioka, T.; Kobayashi, T.; Asada, T.; Kinoshita, H.; Inomata, K. Bull. Chem. Soc. Jpn. 1992, 65, 1379.
83. 3 olefin with sodium amalgam and hydrogenation to the desired product 1 in subsequent steps. The indicated configuration at C-3 of 18 was established by NOE experiments conducted upon its N-Cbz derivative. When H-2 was irradiated (δ 4.58), 10% enhancement of the signal of H-3 (δ 3.48) was observed, while irradiation of H-3 gave 15% enhancement of the H-2 signal. Decoupling experiments of the N-Cbz derivative indicated J = 3.6 Hz between H-2 and H-3, and J = 8.3 and 11.3 Hz between H-3 and the two protons at H-4. These results are consistent with an axial hydrogen atom at C-3 and a cis relationship between H-2 and H-3. The indicated configurations at C-2 of 17 and 18 was confirmed by their respective conversions into the known products 1 and 19. respectively.