Intramolecular Formal Aza-[3 + 3] Cycloaddition Approach to Indoloquinolizidine Alkaloids. A Stereoselective Total Synthesis of (±)-Tangutorine

Organic Letters

Volumn 5, Issue 24, 2003, Pages 4709-4712

  Luo, Shengjun ^a   Zificsak, Craig A ^a   Hsung, Richard P ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID DERIVATIVE; INDOLOQUINOLINE DERIVATIVE; QUINOLIZIDINE DERIVATIVE; TANGUTORINE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CYCLOADDITION; MOLECULAR DYNAMICS; STEREOCHEMISTRY; SYNTHESIS;

ALKALOIDS; AZA COMPOUNDS; CARBOLINES; INDOLEQUINONES; MOLECULAR STRUCTURE; QUINOLIZINES; STEREOISOMERISM;

EID: 0348041988     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol030114q     Document Type: Article

References (71)

1. Duan, J.-A.; Williams, I. D.; Che, C.-T.; Zhou, R.-H., Zhao, S.-X. Tetrahedron Lett. 1999, 40, 2593.
2. (a) Herbert, R. B. In The Monoterpenoid Indole Alkaloids; Saxon, J. E., Ed; Wiley-Interscience: New York, 1994; Supplement to Vol. 25, Part 4 of The Chemistry of Heterocyclic Compounds, Chapter 1.
3. (b) Saxon, J. E. In The Monoterpenoid Indole Alkaloids; Saxon, J. E., Ed; Wiley-Interscience: New York, 1994; Supplement to Vol. 25, Part 4 of The Chemistry of Heterocyclic Compounds, Chapter 8.
4. (c) Saxon, J. E. In The Alkaloids; Cordell, G. A., Ed.; Academic Press: New York, 1998; Vols. 50 and 51.
5. (d) Toyota, M.; Ihara, M. Nat. Prod. Rep. 1998, 75, 327.
6. (e) Scholz, U.; Winterfeldt, E. Nat. Prod. Rep. 2000 17, 349.
7. (+)-Deplancheine (2) was initially isolated from the New Caledonian plant Alstonia deplanchei van Heurck et Mueller Arg. (Apocynaceae). See: (a) Besselièvre, R.; Cosson, H. P.; Das, B. C.; Husson, H. P. Tetrahedron Lett. 1980, 21, 63. For subsequent isolations, see: (b) Petitfrere-Auvray, N.; Vercauteren, J.; Massiot, G.; Lukacs, G.; Sevenet, T.; Le Men-Olivier, L.; Richard, B.; Jacquier, M. J. Phytochemistry 1981, 20, 1987. (c) Robert, G. M. T.; Ahond, A.; Poupat, C.; Potier, P.; Jolles, C.; Jousselin, A.; Jacquemin, H. J. Nat. Prod. 1983, 46, 694. (d) Guillaume, D.; Morfaux, A. M.; Richard, B.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Sevenet, T. Phytochemistry 1984, 23, 2407. (f) Cherif, A.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Labarre, S. Phytochemistry 1989, 28, 667.
8. (+)-Deplancheine (2) was initially isolated from the New Caledonian plant Alstonia deplanchei van Heurck et Mueller Arg. (Apocynaceae). See: (a) Besselièvre, R.; Cosson, H. P.; Das, B. C.; Husson, H. P. Tetrahedron Lett. 1980, 21, 63. For subsequent isolations, see: (b) Petitfrere-Auvray, N.; Vercauteren, J.; Massiot, G.; Lukacs, G.; Sevenet, T.; Le Men-Olivier, L.; Richard, B.; Jacquier, M. J. Phytochemistry 1981, 20, 1987. (c) Robert, G. M. T.; Ahond, A.; Poupat, C.; Potier, P.; Jolles, C.; Jousselin, A.; Jacquemin, H. J. Nat. Prod. 1983, 46, 694. (d) Guillaume, D.; Morfaux, A. M.; Richard, B.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Sevenet, T. Phytochemistry 1984, 23, 2407. (f) Cherif, A.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Labarre, S. Phytochemistry 1989, 28, 667.
9. (+)-Deplancheine (2) was initially isolated from the New Caledonian plant Alstonia deplanchei van Heurck et Mueller Arg. (Apocynaceae). See: (a) Besselièvre, R.; Cosson, H. P.; Das, B. C.; Husson, H. P. Tetrahedron Lett. 1980, 21, 63. For subsequent isolations, see: (b) Petitfrere-Auvray, N.; Vercauteren, J.; Massiot, G.; Lukacs, G.; Sevenet, T.; Le Men-Olivier, L.; Richard, B.; Jacquier, M. J. Phytochemistry 1981, 20, 1987. (c) Robert, G. M. T.; Ahond, A.; Poupat, C.; Potier, P.; Jolles, C.; Jousselin, A.; Jacquemin, H. J. Nat. Prod. 1983, 46, 694. (d) Guillaume, D.; Morfaux, A. M.; Richard, B.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Sevenet, T. Phytochemistry 1984, 23, 2407. (f) Cherif, A.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Labarre, S. Phytochemistry 1989, 28, 667.
10. (+)-Deplancheine (2) was initially isolated from the New Caledonian plant Alstonia deplanchei van Heurck et Mueller Arg. (Apocynaceae). See: (a) Besselièvre, R.; Cosson, H. P.; Das, B. C.; Husson, H. P. Tetrahedron Lett. 1980, 21, 63. For subsequent isolations, see: (b) Petitfrere-Auvray, N.; Vercauteren, J.; Massiot, G.; Lukacs, G.; Sevenet, T.; Le Men-Olivier, L.; Richard, B.; Jacquier, M. J. Phytochemistry 1981, 20, 1987. (c) Robert, G. M. T.; Ahond, A.; Poupat, C.; Potier, P.; Jolles, C.; Jousselin, A.; Jacquemin, H. J. Nat. Prod. 1983, 46, 694. (d) Guillaume, D.; Morfaux, A. M.; Richard, B.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Sevenet, T. Phytochemistry 1984, 23, 2407. (f) Cherif, A.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Labarre, S. Phytochemistry 1989, 28, 667.
11. (+)-Deplancheine (2) was initially isolated from the New Caledonian plant Alstonia deplanchei van Heurck et Mueller Arg. (Apocynaceae). See: (a) Besselièvre, R.; Cosson, H. P.; Das, B. C.; Husson, H. P. Tetrahedron Lett. 1980, 21, 63. For subsequent isolations, see: (b) Petitfrere-Auvray, N.; Vercauteren, J.; Massiot, G.; Lukacs, G.; Sevenet, T.; Le Men-Olivier, L.; Richard, B.; Jacquier, M. J. Phytochemistry 1981, 20, 1987. (c) Robert, G. M. T.; Ahond, A.; Poupat, C.; Potier, P.; Jolles, C.; Jousselin, A.; Jacquemin, H. J. Nat. Prod. 1983, 46, 694. (d) Guillaume, D.; Morfaux, A. M.; Richard, B.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Sevenet, T. Phytochemistry 1984, 23, 2407. (f) Cherif, A.; Massiot, G.; Le Men-Olivier, L.; Pusset, J.; Labarre, S. Phytochemistry 1989, 28, 667.
12. For the most recent syntheses, see: (a) Itoh, T.; Matsuya, Y.; Enomoto, Y.; Ohsawa, A. Heterocycles 2001, 55, 1165. (b) Lounasmaa, M.; Karinen, K.; Tolvanen, A. Heterocycles 1997, 45, 1397. (c) Lounasmaa, M.; Hanhinen, P.; Jokela, R. Heterocycles 1996, 43, 443. (d) Rosenmund, P.; Hosseini-Merescht, M. Liebigs Ann. Chem. 1992, 1321. (e) Sankar, P. J.; Das, S. K.; Giri, V. S. Heterocycles 1991, 32, 1109.
13. For the most recent syntheses, see: (a) Itoh, T.; Matsuya, Y.; Enomoto, Y.; Ohsawa, A. Heterocycles 2001, 55, 1165. (b) Lounasmaa, M.; Karinen, K.; Tolvanen, A. Heterocycles 1997, 45, 1397. (c) Lounasmaa, M.; Hanhinen, P.; Jokela, R. Heterocycles 1996, 43, 443. (d) Rosenmund, P.; Hosseini-Merescht, M. Liebigs Ann. Chem. 1992, 1321. (e) Sankar, P. J.; Das, S. K.; Giri, V. S. Heterocycles 1991, 32, 1109.
14. For the most recent syntheses, see: (a) Itoh, T.; Matsuya, Y.; Enomoto, Y.; Ohsawa, A. Heterocycles 2001, 55, 1165. (b) Lounasmaa, M.; Karinen, K.; Tolvanen, A. Heterocycles 1997, 45, 1397. (c) Lounasmaa, M.; Hanhinen, P.; Jokela, R. Heterocycles 1996, 43, 443. (d) Rosenmund, P.; Hosseini-Merescht, M. Liebigs Ann. Chem. 1992, 1321. (e) Sankar, P. J.; Das, S. K.; Giri, V. S. Heterocycles 1991, 32, 1109.
15. For the most recent syntheses, see: (a) Itoh, T.; Matsuya, Y.; Enomoto, Y.; Ohsawa, A. Heterocycles 2001, 55, 1165. (b) Lounasmaa, M.; Karinen, K.; Tolvanen, A. Heterocycles 1997, 45, 1397. (c) Lounasmaa, M.; Hanhinen, P.; Jokela, R. Heterocycles 1996, 43, 443. (d) Rosenmund, P.; Hosseini-Merescht, M. Liebigs Ann. Chem. 1992, 1321. (e) Sankar, P. J.; Das, S. K.; Giri, V. S. Heterocycles 1991, 32, 1109.
16. For the most recent syntheses, see: (a) Itoh, T.; Matsuya, Y.; Enomoto, Y.; Ohsawa, A. Heterocycles 2001, 55, 1165. (b) Lounasmaa, M.; Karinen, K.; Tolvanen, A. Heterocycles 1997, 45, 1397. (c) Lounasmaa, M.; Hanhinen, P.; Jokela, R. Heterocycles 1996, 43, 443. (d) Rosenmund, P.; Hosseini-Merescht, M. Liebigs Ann. Chem. 1992, 1321. (e) Sankar, P. J.; Das, S. K.; Giri, V. S. Heterocycles 1991, 32, 1109.
17. For a total synthesis of (-)-deplancheine, see: Meyers, A. I.; Sohda, T. ; Loewe, M. F. J. Org. Chem. 1986, 51, 3108.
18. (a) Rapoport, H.; Windgassen, R. J.; Hughes, N. A.; Onak, T. P. J. Am. Chem. Soc. 1960, 82, 4404.
19. (b) Wenkert, E.; Wickberg, B. J. Am. Chem. Soc. 1965, 87, 1580.
20. (a) Deiter, A.; Chen, K.; Eary, T.; Martin, S. F. J. Am. Chem. Soc. 2003, 125, 4541.
21. (b) Fornicola, R. S.; Subburaj, K.; Montgomery, J. Org. Lett. 2002, 4, 615.
22. (c) Yu, S.; Berner, O. M.; Cook, J. M. J. Am. Chem. Soc. 2000, 122, 7827.
23. (d) Martin, S. F.; Chen, K. X.; Eary, C. T. Org. Lett. 1999, 1, 79.
24. (e) Birman, V. B.; Rawal, V. H. Tetrahedron Lett. 1998, 39, 7219.
25. (f) Takayama, H.; Watanabe, F.; Kitajima, M.; Aimi, N. Tetrahedron Lett. 1997, 38, 5307.
26. (g) Martin, S. F.; Benage, B.; Geraci, L. S.; Hunter, J. E.; Mortimore, M. J. Am. Chem. Soc. 1991, 113, 6161.
27. (h) Martin, S. F.; Benage, B.; Hunter, J. E. J. Am. Chem. Soc. 1988, 110, 5925.
28. (i) Yamada, K.; Aoki, K.; Kato, T.; Uemura, D.; van Tamelen, E. E. J. Chem. Soc., Chem. Commun. 1974, 908.
29. (a) Szántay, C.; Blaskò, G.; Honty, K.; Dörnyei, G. In The Alkaloids: Chemistry and Pharmacology; Brossi, A., Ed.; Academic Press: Orlando, 1986; Vol. 27, pp 131-268.
30. (b) Leonard, J. Nat. Prod. Rep. 1999, 16, 319.
31. For some recent elegant examples of application of Pictet-Spengler cyclization, see: (a) Yu, J.; Wang, T.; Liu, X.; Deschamps, J.; Flippen-Anderson, J.; Liao, X.; Cook, J. M. J. Org. Chem. 2003, 68, ASAP. (b) Yu, J.; Wearing, X.; Cook, J. M. Tetrahedron Lett. 2003, 44, 543. (c) Yu, J.; Wang, T.; Wearing, X.; Ma, J.; Cook, J. M. J. Org. Chem. 2003, 68, 5852. (d) Zhao, S.; Liao, X.; Cook, J. M. Org. Lett. 2002, 4, 687.
32. For some recent elegant examples of application of Pictet-Spengler cyclization, see: (a) Yu, J.; Wang, T.; Liu, X.; Deschamps, J.; Flippen-Anderson, J.; Liao, X.; Cook, J. M. J. Org. Chem. 2003, 68, ASAP. (b) Yu, J.; Wearing, X.; Cook, J. M. Tetrahedron Lett. 2003, 44, 543. (c) Yu, J.; Wang, T.; Wearing, X.; Ma, J.; Cook, J. M. J. Org. Chem. 2003, 68, 5852. (d) Zhao, S.; Liao, X.; Cook, J. M. Org. Lett. 2002, 4, 687.
33. For some recent elegant examples of application of Pictet-Spengler cyclization, see: (a) Yu, J.; Wang, T.; Liu, X.; Deschamps, J.; Flippen-Anderson, J.; Liao, X.; Cook, J. M. J. Org. Chem. 2003, 68, ASAP. (b) Yu, J.; Wearing, X.; Cook, J. M. Tetrahedron Lett. 2003, 44, 543. (c) Yu, J.; Wang, T.; Wearing, X.; Ma, J.; Cook, J. M. J. Org. Chem. 2003, 68, 5852. (d) Zhao, S.; Liao, X.; Cook, J. M. Org. Lett. 2002, 4, 687.
34. For some recent elegant examples of application of Pictet-Spengler cyclization, see: (a) Yu, J.; Wang, T.; Liu, X.; Deschamps, J.; Flippen-Anderson, J.; Liao, X.; Cook, J. M. J. Org. Chem. 2003, 68, ASAP. (b) Yu, J.; Wearing, X.; Cook, J. M. Tetrahedron Lett. 2003, 44, 543. (c) Yu, J.; Wang, T.; Wearing, X.; Ma, J.; Cook, J. M. J. Org. Chem. 2003, 68, 5852. (d) Zhao, S.; Liao, X.; Cook, J. M. Org. Lett. 2002, 4, 687.
35. (a) Putkonen, T.; Tolvanen, A.; Jokela, R. Tetrahedron Lett. 2001, 42, 6593.
36. (b) Berner, M.; Tolvanen, A.; Jokela, R. Tetrahedron Lett. 1999, 40, 7119.
37. (c) Putkonen, T.; Tolvanen, A.; Jokela, R.; Caccamese, S.; Parrinello, N. Tetrahedron 2003, 59, 8589.
38. The original structural assignment of tangutorine contained a discrepancy between the actual ChemDraw structure and the X-ray crystallographic structure for the relative stereochemistry at C3-C21.
39. For intermolecular formal aza-[3 + 3] cycloadditions, see: (a) Sklenicka, H. M.; Hsung, R. P.; McLaughlin, M. J.; Wei, L.-L.; Gerasyuto, A. I.; Brennessel, W. W. J. Am. Chem. Soc. 2002, 124, 10435. (b) For a review, see: Hsung, R. P.; Wei, L.-L.; Sklenicka, H. M.; Shen, H. C.; McLaughlin, M. J.; Zehnder, L. R. In Trends in Heterocyclic Chemistry; Research Trends: Poojapura, Trivandrum, India, 2001; Vol. 7, pp 1-24.
40. For intermolecular formal aza-[3 + 3] cycloadditions, see: (a) Sklenicka, H. M.; Hsung, R. P.; McLaughlin, M. J.; Wei, L.-L.; Gerasyuto, A. I.; Brennessel, W. W. J. Am. Chem. Soc. 2002, 124, 10435. (b) For a review, see: Hsung, R. P.; Wei, L.-L.; Sklenicka, H. M.; Shen, H. C.; McLaughlin, M. J.; Zehnder, L. R. In Trends in Heterocyclic Chemistry; Research Trends: Poojapura, Trivandrum, India, 2001; Vol. 7, pp 1-24.
41. (a) Sklenicka, H. M.; Hsung, R. P.; Wei, L.-L.; McLaughlin, M. J.; Gerasyuto, A. I.; Degen, S. J.; Mulder, J. A. Org. Lett. 2000, 2, 1161.
42. (b) Hsung, R. P.; Wei, L.-L.; Sklenicka, H. M.; Douglas, C. J.; McLaughlin, M. J.; Mulder, J. A.; Yao, L. J. Org. Lett. 1999, 1, 509.
43. For a total synthesis of 2-epi-perhydrohistrionicotoxin using intermolecular aza-[3 + 3], see: McLaughlin, M. J.; Hsung, R. P.; Cole, K. C.; Hahn, J. M.; Wang, J. Org. Lett. 2002, 4, 2017.
44. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
45. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
46. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
47. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
48. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
49. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
50. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
51. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
52. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
53. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
54. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
55. For recent studies in this area, see: (a) Abelman, M. M.; Curtis, J. K.; James, D. R. Tetrahedron Lett. 2003, 44, 6527. (b) Hedley, S. J.; Moran, W. J.; Price, D. A.; Harrity, J. P. A. J. Org. Chem. 2003, 68, 4286. (c) Chang, M.-Y.; Lin, J. Y.-C.; Chen, S. T.; Chang, N.-C. J. Chin. Chem. Soc. 2002, 49, 1079. (d) Hedley, S. J.; Moran, W. J.; Prenzel, A. H. G. P.; Price, D. A.; Harrity, J. P. A. Synlett 2001, 1596. (e) Davies, I. W.; Marcoux, J.-F.; Reider, P. J. Org. Lett. 2001, 3, 209. (f) Davies, I. W.; Taylor, M.; Marcoux, J.-F.; Wu, J.; Dormer, P. G.; Hughes, D.; Reider, P. J. J. Org. Chem. 2001, 66, 251. (g) Nemes, P.; Balázs, B.; Tóth, G.; Scheiber, P. Synlett 1999, 222. (h) Hua, D. H.; Chen, Y.; Sin, H.-S.; Robinson, P. D.; Meyers, C. Y.; Perchellet, E. M.; Perchellet, J.-P.; Chiang, P. K.; Biellmann, J.-P. Acta Crystallogr. 1999, C55, 1698. (i) Benovsky, P.; Stephenson, G. A.; Stille, J. R. J. Am. Chem. Soc. 1998, 120, 2493. (j) Heber, D.; Berghaus, Th. J. Heterocycl. Chem. 1994, 31, 1353. (k) Paulvannan, K.; Stille, J. R. Tetrahedron Lett. 1993, 34, 215 and 6677. (l) Paulvannan, K.; Stille, J. R. J. Org. Chem. 1992, 57, 5319.
56. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
57. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
58. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
59. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
60. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
61. For leading references on electrocyclic ring closures involving 1-azatrienes, see: (a) Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763. (b) de Lera, A. R.; Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 4051. (c) Okamura, W. H.; de Lera, A. R.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462. For an earlier account, see: (e) Oppolzer, V. W. Angew. Chem. 1972, 22, 1108. For recent accounts similar to Okamura's studies, see: (f) Tanaka, K.; Mori, H.; Yamamoto, M.; Katsumura, S. J. Org. Chem. 2001, 66, 3099. (g) Tanaka, K.; Katsumura, S. J. Am. Chem. Soc. 2002, 124, 9660.
62. For development of an intramolecular formal aza-[3 + 3] cycloaddition, see: Wei, L.-L.; Sklenicka, H. M.; Gerasyuto, A. I.; Hsung, R. P. Angew. Chem., Int. Ed. 2001, 40, 1516.
63. Kobayashi, S.; Ueda, T.; Fukuyama, T. Synlett 2000, 883.
64. 13C NMR, FTIR, and mass spectroscopy.
65. (a) Chu, L.; Fisher, M. H.; Goulet, M. T.; Wyvratt, M. J. Tetrahedron Lett. 1997, 38, 3871.
66. (b) Osby, J. O.; Martin, M. G.; Ganem, B. Tetrahedron Lett. 1984, 25, 2093.
67. The desired pentacycle 9 often contained impurities but could be unambiguous assigned and fully characterized when its endo-cyclic olefin was hydrogenated to give 25 (see in the later scheme).
68. Mander, L. N.; Sethi, S. P. Tetrahedron Lett. 1983, 24, 5425.
69. Bartoli, G.; Cimarelli, C.; Palmieri, G. J. Chem. Soc., Perkin Trans. 1 1994, 537.
70. Paikh, J. R.; Doering, W. von E. J. Am. Chem. Soc. 1967, 89, 5507.
71. 1H NMR resonances.