Palladium(0)-catalyzed heteroarylation of 2- and 3-indolylzinc derivatives. An efficient general method for the preparation of (2-pyridyl)indoles and their application to indole alkaloid synthesis

Journal of Organic Chemistry

Volumn 62, Issue 10, 1997, Pages 3158-3175

  Amat, Mercedes ^a   Hadida, Sabine ^a   Pshenichnyi, Grigorii ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

INDOLE ALKALOID; INDOLE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030911153     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo962169u     Document Type: Article

References (140)

1. (a) Bisset, N. G. In Indole and Biogenetically Related Alkaloids; Phillipson, J. D., Zenk, M. H., Eds.; Academic Press: London, 1980; Chapter 3.
2. (b) Herbert, R. B. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 1.
3. Atta-ur-Rahman; Basha, A. Biosynthesis of Indole Alkaloids; Clarendon Press: Oxford, 1983.
4. (a) Kisakürek, M. V.; Leeuwenberg, A. J. M.; Hesse, M. In Alkaloids: Chemical and Biological Perspectives; Pelletier, S. W., Ed.; Wiley: New York, 1983; Vol. 1, Chapter 5.
5. (b) Kisakürek, M. V.; Hesse, M. In Indole and Biogenetically Related Alkaloids; Phillipson, J. D., Zenk, M. H., Eds.; Academic Press: London, 1980; Chapter 2.
6. 2-(2-Pyridyl)indoles: (a) Sugasawa, S.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1956, 4, 16. (b) Caixach, J.; Capell, R.; Gálvez, C.; González, A.; Roca, N. J. Heterocycl. Chem. 1979, 16, 1631. (c) Crotti, C.; Cenini, S.; Rindone, B.; Tollari, S.; Demartin, F. J. Chem. Soc., Chem. Commun. 1986, 784. (d) Gribble, G. W.; Johnson, D. A. Tetrahedron Lett. 1987, 28, 5259. (e) Seki, K.; Ohkura, K.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1988, 36, 940.
7. 2-(2-Pyridyl)indoles: (a) Sugasawa, S.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1956, 4, 16. (b) Caixach, J.; Capell, R.; Gálvez, C.; González, A.; Roca, N. J. Heterocycl. Chem. 1979, 16, 1631. (c) Crotti, C.; Cenini, S.; Rindone, B.; Tollari, S.; Demartin, F. J. Chem. Soc., Chem. Commun. 1986, 784. (d) Gribble, G. W.; Johnson, D. A. Tetrahedron Lett. 1987, 28, 5259. (e) Seki, K.; Ohkura, K.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1988, 36, 940.
8. 2-(2-Pyridyl)indoles: (a) Sugasawa, S.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1956, 4, 16. (b) Caixach, J.; Capell, R.; Gálvez, C.; González, A.; Roca, N. J. Heterocycl. Chem. 1979, 16, 1631. (c) Crotti, C.; Cenini, S.; Rindone, B.; Tollari, S.; Demartin, F. J. Chem. Soc., Chem. Commun. 1986, 784. (d) Gribble, G. W.; Johnson, D. A. Tetrahedron Lett. 1987, 28, 5259. (e) Seki, K.; Ohkura, K.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1988, 36, 940.
9. 2-(2-Pyridyl)indoles: (a) Sugasawa, S.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1956, 4, 16. (b) Caixach, J.; Capell, R.; Gálvez, C.; González, A.; Roca, N. J. Heterocycl. Chem. 1979, 16, 1631. (c) Crotti, C.; Cenini, S.; Rindone, B.; Tollari, S.; Demartin, F. J. Chem. Soc., Chem. Commun. 1986, 784. (d) Gribble, G. W.; Johnson, D. A. Tetrahedron Lett. 1987, 28, 5259. (e) Seki, K.; Ohkura, K.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1988, 36, 940.
10. 2-(2-Pyridyl)indoles: (a) Sugasawa, S.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1956, 4, 16. (b) Caixach, J.; Capell, R.; Gálvez, C.; González, A.; Roca, N. J. Heterocycl. Chem. 1979, 16, 1631. (c) Crotti, C.; Cenini, S.; Rindone, B.; Tollari, S.; Demartin, F. J. Chem. Soc., Chem. Commun. 1986, 784. (d) Gribble, G. W.; Johnson, D. A. Tetrahedron Lett. 1987, 28, 5259. (e) Seki, K.; Ohkura, K.; Terashima, M.; Kanaoka, Y. Chem. Pharm. Bull. 1988, 36, 940.
11. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
12. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
13. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
14. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
15. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
16. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
17. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
18. 3-(2-Pyridyl)indoles: (a) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1986, 99. (b) Naito, T.; Iida, N.; Ninomiya, I. J. Chem. Soc., Chem. Commun. 1981, 44. (c) Suzuki, T.; Sato, E.; Goto, K.; Unno, K; Kametani, T. Heterocycles 1980, 14, 433. (d) Kametani, T.; Suzuki, T. J. Chem. Soc. (C) 1971, 1053. (e) Kametani, T.; Suzuki, T. Chem. Pharm. Bull. 1971, 19, 1424. (f) Kametani, T.; Suzuki, T. J. Org. Chem. 1971, 36, 1291. (g) Hamana, M.; Kumadaki, I. Chem. Pharm. Bull. 1970, 18, 1742. (h) Powers, J. C. J. Org. Chem. 1965, 30, 2534.
19. For a review on the formation of C-C bonds in heterocycles using Pd-catalyzed reactions, see: Kalinin, V. N. Synthesis 1992, 413.
20. (a) For a review on transition metal catalyzed reactions of organozinc reagents, see: Erdik, E. Tetrahedron 1992, 48, 9577. (b) For a review on the preparation and reactions of polyfunctional organozinc reagents, see: Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117.
21. (a) For a review on transition metal catalyzed reactions of organozinc reagents, see: Erdik, E. Tetrahedron 1992, 48, 9577. (b) For a review on the preparation and reactions of polyfunctional organozinc reagents, see: Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117.
22. (a) This part of the work was presented in a preliminary form at the Eight European Symposium on Organic Chemistry (ESOC-8), Sitges, Spain, August 1993.
23. For preliminary reports, see: (b) Amat, M.; Hadida, S.; Bosch, J. Tetrahedron Lett. 1993, 34, 5005. (c) Amat, M.; Hadida, S,; Bosch, J. Tetrahedron Lett. 1994, 35, 793.
24. For preliminary reports, see: (b) Amat, M.; Hadida, S.; Bosch, J. Tetrahedron Lett. 1993, 34, 5005. (c) Amat, M.; Hadida, S,; Bosch, J. Tetrahedron Lett. 1994, 35, 793.
25. Vincent, P.; Beaucourt, J. P.; Pichat, L. Tetrahedron Lett. 1984, 25, 201.
26. 9b halides were reported: (a) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Heterocycles 1993, 36, 941. (b) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Tetrahedron Lett. 1993, 34, 5955. The full paper of these studies has recently been published: (c) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. J. Chem. Soc., Perkin Trans. 1 1996, 1927.
27. 9b halides were reported: (a) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Heterocycles 1993, 36, 941. (b) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Tetrahedron Lett. 1993, 34, 5955. The full paper of these studies has recently been published: (c) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. J. Chem. Soc., Perkin Trans. 1 1996, 1927.
28. 9b halides were reported: (a) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Heterocycles 1993, 36, 941. (b) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. Tetrahedron Lett. 1993, 34, 5955. The full paper of these studies has recently been published: (c) Sakamoto, T.; Kondo, Y.; Takazawa, N.; Yamanaka, H. J. Chem. Soc., Perkin Trans. 1 1996, 1927.
29. For the preparation and reactions of lithium indolyl(dimethyl)zincates, see: Kondo, Y.; Takazawa, N.; Yoshida, A.; Sakamoto, T. J. Chem. Soc., Perkin Trans. 1 1995, 1207.
30. For reviews, see: (a) Hegedus, L. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 1113. (b) Martin, A. R.; Zheng, Q. In Advances in Nitrogen Heterocycles; Pearson, W. H., Ed.; JAI Press, Inc.: Greenwich, 1990; Vol. 1, pp 71-120.
31. For reviews, see: (a) Hegedus, L. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 1113. (b) Martin, A. R.; Zheng, Q. In Advances in Nitrogen Heterocycles; Pearson, W. H., Ed.; JAI Press, Inc.: Greenwich, 1990; Vol. 1, pp 71-120.
32. Widdowson, D. A.; Zhang, Y.-Z. Tetrahedron 1986, 42, 2111.
33. (a) Minato, A.; Tamao, K.; Hayashi, T.; Suzuki, K.; Kumada, M. Tetrahedron Lett. 1981, 22, 5319.
34. (b) Minato, A.; Suzuki, K.; Tamao, K.; Kumada, M. J. Chem. Soc., Chem. Commun. 1984, 511.
35. Ishikura, M.; Terashima, M. J. Chem. Soc., Chem. Commun. 1989, 135.
36. For Pd-catalyzed cross-coupling reactions of indole itself or substituted indoles with chloropyrazines, see: (a) Akita, Y.; Inoue, A.; Yamamoto, K.; Ohta, A. Heterocycles 1985, 23, 2327. (b) Akita, Y.; Itagaki, Y.; Takizawa, S.; Ohta, A. Chem. Pharm. Bull. 1989, 37, 1477.
37. For Pd-catalyzed cross-coupling reactions of indole itself or substituted indoles with chloropyrazines, see: (a) Akita, Y.; Inoue, A.; Yamamoto, K.; Ohta, A. Heterocycles 1985, 23, 2327. (b) Akita, Y.; Itagaki, Y.; Takizawa, S.; Ohta, A. Chem. Pharm. Bull. 1989, 37, 1477.
38. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
39. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
40. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
41. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
42. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
43. 2-Indolylstannanes: (a) Palmisano, G.; Santagostino, M. Synlett 1993, 771. (b) Palmisano, G.; Santagostino, M. Helv. Chim. Acta 1993, 76, 2356. (c) Fukuyama, T.; Chen, X.; Peng, G. J. Am. Chem. Soc. 1994, 116, 3127. (d) Labadie, S. S.; Teng, E. J. Org. Chem. 1994, 59, 4250. (e) Hudkins, R. L.; Diebold, J. L.; Marsh, F. D. J. Org. Chem. 1995, 60, 6218. 3-Indolylstannanes: (f) Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1994, 35, 2405.
44. For recent examples using 3-indolylboronic acids, see: (a) Kawasaki, I.; Yamashita, M.; Ohta, S. Chem. Pharm. Bull. 1996, 44, 1831. Pd-catalyzed cross-coupling reactions of haloindoles with heteroaryl organometallics have received less attention: (b) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (c) Somei, M.; Sayama, S.; Naka, K.; Yamada, F. Heterocycles 1988, 27, 1585. Yang, Y.; Martin, A. R. Synth. Commun. 1992, 22, 1757.
45. For recent examples using 3-indolylboronic acids, see: (a) Kawasaki, I.; Yamashita, M.; Ohta, S. Chem. Pharm. Bull. 1996, 44, 1831. Pd-catalyzed cross-coupling reactions of haloindoles with heteroaryl organometallics have received less attention: (b) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (c) Somei, M.; Sayama, S.; Naka, K.; Yamada, F. Heterocycles 1988, 27, 1585. Yang, Y.; Martin, A. R. Synth. Commun. 1992, 22, 1757.
46. For recent examples using 3-indolylboronic acids, see: (a) Kawasaki, I.; Yamashita, M.; Ohta, S. Chem. Pharm. Bull. 1996, 44, 1831. Pd-catalyzed cross-coupling reactions of haloindoles with heteroaryl organometallics have received less attention: (b) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (c) Somei, M.; Sayama, S.; Naka, K.; Yamada, F. Heterocycles 1988, 27, 1585. Yang, Y.; Martin, A. R. Synth. Commun. 1992, 22, 1757.
47. For recent examples using 3-indolylboronic acids, see: (a) Kawasaki, I.; Yamashita, M.; Ohta, S. Chem. Pharm. Bull. 1996, 44, 1831. Pd-catalyzed cross-coupling reactions of haloindoles with heteroaryl organometallics have received less attention: (b) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (c) Somei, M.; Sayama, S.; Naka, K.; Yamada, F. Heterocycles 1988, 27, 1585. Yang, Y.; Martin, A. R. Synth. Commun. 1992, 22, 1757.
48. Saulnier, M. G.; Gribble, G. W. J. Org. Chem. 1982, 47, 757.
49. Wenkert, E.; Angell, E. C.; Ferreira, V. F.; Michelotti, E. L.; Piettre, S. R.; Sheu, J.-H.; Swindell, C. S. J. Org. Chem. 1986, 51, 2343.
50. A similar result was reported in refs 9b and 9c. To avoid this inconvenience, the authors prepared (1-(benzenesulfonyl)-3-indolyl)zinc iodide by oxidative addition of active zinc to the corresponding 3-iodoindole.
51. (a) Sundberg, R. J.; Russell, H. F. J. Org. Chem. 1973, 38, 3324.
52. (b) Beswick, P. J.; Greenwood, C. S.; Mowlem, T. J.; Nechvatal, G.; Widdowson, D. A. Tetrahedron 1988, 44, 7325.
53. (c) Iwao, M. Heterocycles 1993, 36, 29.
54. For the preparation of 1-silyl-3-lithioindoles and their reactions with a variety of electrophilic reagents to regioselectively give 3-substituted indoles, see: (a) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. J. Org. Chem. 1994, 59, 10. (b) Amat, M.; Sathyanarayana, S.; Hadida, S.; Bosch, J. Heterocycles 1996, 43, 1713. (c) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. Org. Synth. 1997, 74, 248. See also ref 17a.
55. For the preparation of 1-silyl-3-lithioindoles and their reactions with a variety of electrophilic reagents to regioselectively give 3-substituted indoles, see: (a) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. J. Org. Chem. 1994, 59, 10. (b) Amat, M.; Sathyanarayana, S.; Hadida, S.; Bosch, J. Heterocycles 1996, 43, 1713. (c) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. Org. Synth. 1997, 74, 248. See also ref 17a.
56. For the preparation of 1-silyl-3-lithioindoles and their reactions with a variety of electrophilic reagents to regioselectively give 3-substituted indoles, see: (a) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. J. Org. Chem. 1994, 59, 10. (b) Amat, M.; Sathyanarayana, S.; Hadida, S.; Bosch, J. Heterocycles 1996, 43, 1713. (c) Amat, M.; Hadida, S.; Sathyanarayana, S.; Bosch, J. Org. Synth. 1997, 74, 248. See also ref 17a.
57. (a) Negishi, E.; King, A. O.; Okukado, N. J. Org. Chem. 1977, 42, 1821.
58. (b) Negishi, E. Acc. Chem. Res. 1982, 15, 340.
59. For reviews, see: (a) Brown, R. T. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 3. (b) Saxton, J. E. Ibid., Chapter 9. (c) Lounasmaa, M.; Tolvanen, A. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 3.
60. For reviews, see: (a) Brown, R. T. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 3. (b) Saxton, J. E. Ibid., Chapter 9. (c) Lounasmaa, M.; Tolvanen, A. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 3.
61. For reviews, see: (a) Brown, R. T. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 3. (b) Saxton, J. E. Ibid., Chapter 9. (c) Lounasmaa, M.; Tolvanen, A. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 3.
62. Szántay, C. Ibid., Chapter 9.
63. (a) Rubiralta, M.; Diez, A.; Bosch, J.; Solans, X. J. Org. Chem. 1989, 54, 5591.
64. (b) Rubiralta, M.; Diez, A.; Vila, C. Tetrahedron 1990, 46, 4443.
65. For a review, see: Gribble, G. W. In Studies in Natural Products Chemistry; Atta-ur-Rahman, Ed; Elsevier: Amsterdam, 1988; Vol. 1, pp 123-168.
66. (a) De Lucchi, O.; Miotti, U.; Modena, G. Org. React. 1991, 40, 157.
67. (b) Grierson, D. S.; Husson, H.-P. In Comprehensive Organic Synthesis; Trost, B. M., Ed; Pergamon Press: Oxford, 1991; Vol. 6, Chapter 4.7.
68. (c) Kennedy, M.; McKervey, M. A. Ibid., Vol. 7, Chapter 2.4.
69. (a) Smallcombe, S. H.; Caserio, M. C. J. Am. Chem. Soc. 1971, 93, 5826.
70. (b) Trost, B. M.; Murayama, E. J. Am. Chem. Soc. 1981, 103, 6529.
71. (c) Trost, B. M.; Murayama, E. Tetrahedron Lett. 1982, 23, 1047.
72. (d) Trost, B. M.; Sato, T. J. Am. Chem. Soc. 1985, 107, 719.
73. (a) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299.
74. (b) Amat, M.; Bosch, J. J. Org. Chem. 1992, 57, 5792.
75. For a preliminary report of this part of the work, see: Amat, M.; Hadida, S.; Sathyanarayana, S; Bosch, J. Tetrahedron Lett. 1996, 37, 3071.
76. 2 in refluxing toluene, the N-ethoxycarbonyl derivative 14 was formed.
77. Le Men, J.; Taylor, W. I. Experientia 1965, 21, 508.
78. Similar N-dealkylations have been observed from β-amino sulfoxides under Pummerer reaction conditions: see ref 29b. For related N-dealkylations of aminoacetaldehyde derivatives, see: (a) Lathbury, D. C.; Parsons, P. J.; Pinto, I. J. Chem. Soc., Chem. Commun. 1988, 81. (b) Mehmandoust, M.; Marazano, C.; Das, B. C. J. Chem. Soc., Chem. Commun. 1989, 1185. (c) Valls, N.; Segarra, V. M.; Maillo, L. C.; Bosch, J. Tetrahedron 1991, 47, 1065. (d) Bosch, J.; Salas, M.; Amat, M.; Alvarez, M.; Morgó, I.; Adrover, B. Tetrahedron 1991, 47, 5269. See also ref 29a.
79. Similar N-dealkylations have been observed from β-amino sulfoxides under Pummerer reaction conditions: see ref 29b. For related N-dealkylations of aminoacetaldehyde derivatives, see: (a) Lathbury, D. C.; Parsons, P. J.; Pinto, I. J. Chem. Soc., Chem. Commun. 1988, 81. (b) Mehmandoust, M.; Marazano, C.; Das, B. C. J. Chem. Soc., Chem. Commun. 1989, 1185. (c) Valls, N.; Segarra, V. M.; Maillo, L. C.; Bosch, J. Tetrahedron 1991, 47, 1065. (d) Bosch, J.; Salas, M.; Amat, M.; Alvarez, M.; Morgó, I.; Adrover, B. Tetrahedron 1991, 47, 5269. See also ref 29a.
80. Similar N-dealkylations have been observed from β-amino sulfoxides under Pummerer reaction conditions: see ref 29b. For related N-dealkylations of aminoacetaldehyde derivatives, see: (a) Lathbury, D. C.; Parsons, P. J.; Pinto, I. J. Chem. Soc., Chem. Commun. 1988, 81. (b) Mehmandoust, M.; Marazano, C.; Das, B. C. J. Chem. Soc., Chem. Commun. 1989, 1185. (c) Valls, N.; Segarra, V. M.; Maillo, L. C.; Bosch, J. Tetrahedron 1991, 47, 1065. (d) Bosch, J.; Salas, M.; Amat, M.; Alvarez, M.; Morgó, I.; Adrover, B. Tetrahedron 1991, 47, 5269. See also ref 29a.
81. Similar N-dealkylations have been observed from β-amino sulfoxides under Pummerer reaction conditions: see ref 29b. For related N-dealkylations of aminoacetaldehyde derivatives, see: (a) Lathbury, D. C.; Parsons, P. J.; Pinto, I. J. Chem. Soc., Chem. Commun. 1988, 81. (b) Mehmandoust, M.; Marazano, C.; Das, B. C. J. Chem. Soc., Chem. Commun. 1989, 1185. (c) Valls, N.; Segarra, V. M.; Maillo, L. C.; Bosch, J. Tetrahedron 1991, 47, 1065. (d) Bosch, J.; Salas, M.; Amat, M.; Alvarez, M.; Morgó, I.; Adrover, B. Tetrahedron 1991, 47, 5269. See also ref 29a.
82. There are very few examples of normal Pummerer cyclizations from β-amino sulfoxides: (a) Pyne, S. G.; Dikic, B. J. Org. Chem. 1090, 55, 1932. (b) Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1992, 48, 7803. (c) Takano, S.; Iida, H.; Inomata, K.; Ogasawara, K. Heterocycles 1993, 35, 47. (d) Bonjoch, J.; Catena, J.; Valls, N. J. Org. Chem. 1996, 61, 7106. See also ref 29b.
83. There are very few examples of normal Pummerer cyclizations from β-amino sulfoxides: (a) Pyne, S. G.; Dikic, B. J. Org. Chem. 1090, 55, 1932. (b) Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1992, 48, 7803. (c) Takano, S.; Iida, H.; Inomata, K.; Ogasawara, K. Heterocycles 1993, 35, 47. (d) Bonjoch, J.; Catena, J.; Valls, N. J. Org. Chem. 1996, 61, 7106. See also ref 29b.
84. There are very few examples of normal Pummerer cyclizations from β-amino sulfoxides: (a) Pyne, S. G.; Dikic, B. J. Org. Chem. 1090, 55, 1932. (b) Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1992, 48, 7803. (c) Takano, S.; Iida, H.; Inomata, K.; Ogasawara, K. Heterocycles 1993, 35, 47. (d) Bonjoch, J.; Catena, J.; Valls, N. J. Org. Chem. 1996, 61, 7106. See also ref 29b.
85. There are very few examples of normal Pummerer cyclizations from β-amino sulfoxides: (a) Pyne, S. G.; Dikic, B. J. Org. Chem. 1090, 55, 1932. (b) Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1992, 48, 7803. (c) Takano, S.; Iida, H.; Inomata, K.; Ogasawara, K. Heterocycles 1993, 35, 47. (d) Bonjoch, J.; Catena, J.; Valls, N. J. Org. Chem. 1996, 61, 7106. See also ref 29b.
86. For a preliminary communication of this and a related abnormal Pummerer cyclization on the indole ring, see: Amat, M.; Bennasar, M.-L.; Hadida, S.; Sufi, B. A.; Zulaica, E.; Bosch, J. Tetrahedron Lett. 1996, 37, 5217.
87. (a) For a similar migration of an arylthio group to an electron-rich aromatic ring under Pummerer reaction conditions, see: Pyne, S. G.; Hajipour, A. R. Tetrahedron 1994, 50, 13501. For related processes, see: (b) Kaneko, T. J. Am. Chem. Soc. 1985, 107, 5490. (c) Terauchi, H.; Tanitame, A.; Tada, K.; Nishikawa, Y. Heterocycles 1996, 43, 1719. (d) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375. (e) Bravo, P.; Capelli, S.; Meille, S. V.; Seresini, P.; Volonterio, A.; Zanda, M. Tetrahedron: Asymmetry 1996, 7, 2321.
88. (a) For a similar migration of an arylthio group to an electron-rich aromatic ring under Pummerer reaction conditions, see: Pyne, S. G.; Hajipour, A. R. Tetrahedron 1994, 50, 13501. For related processes, see: (b) Kaneko, T. J. Am. Chem. Soc. 1985, 107, 5490. (c) Terauchi, H.; Tanitame, A.; Tada, K.; Nishikawa, Y. Heterocycles 1996, 43, 1719. (d) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375. (e) Bravo, P.; Capelli, S.; Meille, S. V.; Seresini, P.; Volonterio, A.; Zanda, M. Tetrahedron: Asymmetry 1996, 7, 2321.
89. (a) For a similar migration of an arylthio group to an electron-rich aromatic ring under Pummerer reaction conditions, see: Pyne, S. G.; Hajipour, A. R. Tetrahedron 1994, 50, 13501. For related processes, see: (b) Kaneko, T. J. Am. Chem. Soc. 1985, 107, 5490. (c) Terauchi, H.; Tanitame, A.; Tada, K.; Nishikawa, Y. Heterocycles 1996, 43, 1719. (d) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375. (e) Bravo, P.; Capelli, S.; Meille, S. V.; Seresini, P.; Volonterio, A.; Zanda, M. Tetrahedron: Asymmetry 1996, 7, 2321.
90. (a) For a similar migration of an arylthio group to an electron-rich aromatic ring under Pummerer reaction conditions, see: Pyne, S. G.; Hajipour, A. R. Tetrahedron 1994, 50, 13501. For related processes, see: (b) Kaneko, T. J. Am. Chem. Soc. 1985, 107, 5490. (c) Terauchi, H.; Tanitame, A.; Tada, K.; Nishikawa, Y. Heterocycles 1996, 43, 1719. (d) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375. (e) Bravo, P.; Capelli, S.; Meille, S. V.; Seresini, P.; Volonterio, A.; Zanda, M. Tetrahedron: Asymmetry 1996, 7, 2321.
91. (a) For a similar migration of an arylthio group to an electron-rich aromatic ring under Pummerer reaction conditions, see: Pyne, S. G.; Hajipour, A. R. Tetrahedron 1994, 50, 13501. For related processes, see: (b) Kaneko, T. J. Am. Chem. Soc. 1985, 107, 5490. (c) Terauchi, H.; Tanitame, A.; Tada, K.; Nishikawa, Y. Heterocycles 1996, 43, 1719. (d) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375. (e) Bravo, P.; Capelli, S.; Meille, S. V.; Seresini, P.; Volonterio, A.; Zanda, M. Tetrahedron: Asymmetry 1996, 7, 2321.
92. For the isolation of 3-(dimethylsulfonio)indolides, see: (a) Daves, G. D., Jr.; Anderson, W. R., Jr.; Pickering, M. V. J. Chem. Soc., Chem. Commun. 1974, 301. (b) Hocker, J.; Ley, K.; Merten, R. Synthesis 1975, 334. (c) Park, K. H.; Gray, G. A.; Daves, G. D., Jr. J. Am. Chem. Soc. 1978, 100, 7475.
93. For the isolation of 3-(dimethylsulfonio)indolides, see: (a) Daves, G. D., Jr.; Anderson, W. R., Jr.; Pickering, M. V. J. Chem. Soc., Chem. Commun. 1974, 301. (b) Hocker, J.; Ley, K.; Merten, R. Synthesis 1975, 334. (c) Park, K. H.; Gray, G. A.; Daves, G. D., Jr. J. Am. Chem. Soc. 1978, 100, 7475.
94. For the isolation of 3-(dimethylsulfonio)indolides, see: (a) Daves, G. D., Jr.; Anderson, W. R., Jr.; Pickering, M. V. J. Chem. Soc., Chem. Commun. 1974, 301. (b) Hocker, J.; Ley, K.; Merten, R. Synthesis 1975, 334. (c) Park, K. H.; Gray, G. A.; Daves, G. D., Jr. J. Am. Chem. Soc. 1978, 100, 7475.
95. 30 gave barely reproducible results, and in most runs, methoxycarbonylation also occurred at the methine carbon of the malonate moiety.
96. Grierson, D. S.; Vuilhorgne, M.; Husson, H.-P. J. Org. Chem. 1982, 47, 4439.
97. For a recent application of these concepts to the synthesis of geissoschizine, see: Bennasar, M.-L.; Jiménez, J.-M.; Sufi, B. A.; Bosch, J. Tetrahedron Lett. 1996, 37, 9105.
98. For previous unsuccessful attempts, see: Bennasar, M.-L.; Zulaica, E.; Sufi, B. A.; Bosch, J. Tetrahedron 1996, 52, 8601. See also ref 42.
99. Oikawa, Y.; Yonemitsu, O. J. Org. Chem. 1976, 41, 1118.
100. Gallagher, T.; Magnus, P.; Huffman, J. C. J. Am. Chem. Soc. 1983, 105, 4750. See also refs 29b and 34d.
101. Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
102. For related cyclizations of N-(2-oxoethyl)piperidine derivatives in the construction of the seven-membered C ring of Iboga alkaloids, see: (a) Sundberg, R. J.; Amat, M.; Fernando, A. J. Org. Chem. 1987, 52, 3151. (b) Sundberg, R. J.; Gadamasetti, K. G. Tetrahedron 1991, 47, 5673.
103. For related cyclizations of N-(2-oxoethyl)piperidine derivatives in the construction of the seven-membered C ring of Iboga alkaloids, see: (a) Sundberg, R. J.; Amat, M.; Fernando, A. J. Org. Chem. 1987, 52, 3151. (b) Sundberg, R. J.; Gadamasetti, K. G. Tetrahedron 1991, 47, 5673.
104. For a preliminary report of this part of the work, see: Amat, M.; Sathyanarayana, S.; Hadida, S.; Bosch, J. Tetrahedron Lett. 1994, 35, 7123.
105. All attempts to directly oxidize the methyl substituent of 8c were unsuccessful.
106. 13C NMR data with the data of the cis and trans isomers of methyl 2-(3-indolyl)-4-piperidinecarboxylate: see ref 46.
107. (a) Amat, M.; Hadida, S.; Llor, N.; Sathyanarayana, S.; Bosch, J. J. Org. Chem. 1996, 61, 3878.
108. For the cyclization of a mixture of 34 and other stereoisomers, see: (b) Bosch, J.; Rubiralta, M.; Domingo, A.; Bolós, J.; Linares, A.; Minguillón, C.; Amat, M.; Bonjoch, J. J. Org. Chem. 1985, 50, 1516.
109. Minor amounts of the C-20 epimer were also isolated. For a detailed discussion of this epimerization and related epimerizations in 3-(2-piperidyl)indoles, see ref 49a.
110. For recent reviews on the Strychnos alkaloids, see: (a) Sapi, J.; Massiot, G. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 7. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids; Cordell, G. A., Ed.; Academic Press: New York, 1996; Vol. 48, pp 75-189.
111. For recent reviews on the Strychnos alkaloids, see: (a) Sapi, J.; Massiot, G. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 7. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids; Cordell, G. A., Ed.; Academic Press: New York, 1996; Vol. 48, pp 75-189.
112. (a) Gràcia, J.; Casamitjana, N.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1994, 59, 3939.
113. (b) Blechert, S. Liebigs Ann. Chem. 1985, 2073.
114. (c) Borris, R. P.; Lankin, D. C.; Cordell, G. A. J. Nat. Prod. 1983, 46, 206.
115. (d) Jackson, A.; Wilson, N. D. V.; Gaskell, A. J.; Joule, J. A. J. Chem. Soc. (C) 1969, 2738.
116. (e) Joule, J. A.; Ohashi, M.; Gilbert, B.; Djerassi, C. Tetrahedron 1965, 21, 1717.
117. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 6. (b) Alvarez, M.; Joule, J. A. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 6.
118. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, Chapter 6. (b) Alvarez, M.; Joule, J. A. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, Chapter 6.
119. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids: Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, pp 244-264. (b) Alvarez, M.; Joule, J. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, pp 248-259. For more recent work, see: (c) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. J. Org. Chem. 1996, 61, 1239. (d) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. Tetrahedron Lett. 1996, 37, 6611.
120. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids: Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, pp 244-264. (b) Alvarez, M.; Joule, J. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, pp 248-259. For more recent work, see: (c) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. J. Org. Chem. 1996, 61, 1239. (d) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. Tetrahedron Lett. 1996, 37, 6611.
121. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids: Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, pp 244-264. (b) Alvarez, M.; Joule, J. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, pp 248-259. For more recent work, see: (c) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. J. Org. Chem. 1996, 61, 1239. (d) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. Tetrahedron Lett. 1996, 37, 6611.
122. For reviews, see: (a) Joule, J. A. In Indoles, The Monoterpenoid Indole Alkaloids: Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, pp 244-264. (b) Alvarez, M.; Joule, J. In Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, pp 248-259. For more recent work, see: (c) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. J. Org. Chem. 1996, 61, 1239. (d) Bennasar, M.-L.; Zulaica, E.; Ramírez, A.; Bosch, J. Tetrahedron Lett. 1996, 37, 6611.
123. For a preliminary report on this part of the work, see: Amat, M.; Hadida, S.; Bosch, J. An. Quim., Int. Ed. 1996, 92, 62.
124. For precedents on the synthesis of hexahydro-1,5-methanoazocino[3,4-6]indoles, see: (a) Dolby, L. J.; Nelson, S. J. J. Org. Chem. 1973, 38, 2882. (b) Bennasar, M.-L.; Alvarez, M.; Lavilla, R.; Zulaica, E.; Bosch, J. J. Org. Chem. 1990, 55, 1156. See also ref 54c.
125. For precedents on the synthesis of hexahydro-1,5-methanoazocino[3,4-6]indoles, see: (a) Dolby, L. J.; Nelson, S. J. J. Org. Chem. 1973, 38, 2882. (b) Bennasar, M.-L.; Alvarez, M.; Lavilla, R.; Zulaica, E.; Bosch, J. J. Org. Chem. 1990, 55, 1156. See also ref 54c.
126. (a) Jackson, A. H.; Naidoo, B. J. Chem. Soc., Perkin Trans. 2 1973, 548 and previous papers in this series.
127. (b) Ganesan, A.; Heathcock, C. H. Tetrahedron Lett. 1993, 34, 439.
128. (c) Diez, A.; Vila, C.; Sinibaldi, M.-E.; Troin, Y.; Rubiralta, M. Tetrahedron Lett. 1993, 34, 733.
129. For a review, see: Ungemach, F.; Cook, J. M. Heterocycles 1978, 9, 1089.
130. For related processes, see; (a) Wenkert, E.; Halls, T. D. J.; Kwart, L. D.; Magnusson, G.; Showalter, H. D. H. Tetrahedron 1981, 37, 4017. (b) Kalaus, G.; Malkieh, N.; Katona, I.; Kajtár-Peredy, M.; Koritsánszky, T.; Kálmán, A.; Szabó, L.; Szántay, C. J. Org. Chem. 1985, 50, 3760.
131. For related processes, see; (a) Wenkert, E.; Halls, T. D. J.; Kwart, L. D.; Magnusson, G.; Showalter, H. D. H. Tetrahedron 1981, 37, 4017. (b) Kalaus, G.; Malkieh, N.; Katona, I.; Kajtár-Peredy, M.; Koritsánszky, T.; Kálmán, A.; Szabó, L.; Szántay, C. J. Org. Chem. 1985, 50, 3760.
132. (a) Bosch, J.; Canals, C.; Granados, R. An. Quim. 1978, 74, 985.
133. (b) Case, F. H. J. Am. Chem. Soc. 1946, 68, 2574.
134. Seide, O. Chem. Ber. 1924, 57, 791.
135. 2.
136. 2 in 78% and 95% yields, respectively.
137. 3 (11 mL).
138. From the synthetic standpoint it was more convenient to use a mixture of bromopyridines 2c and 2d in the cross-coupling reaction, because pyridylindoles 8c and 8d could be separated by column chromatography (AcOEt) much more efficiently than 2c and 2d.
139. 3), 123.5 (CH), 137.1 (C), 138.5 (C), 151.3 (CH), 151.6 (C), 164.6 (C).
140. Bergman, J. Acta Chem. Scand. 1971, 25, 1277.