Diastereoselective Synthesis of Cycloalkylamines by Samarium Diiodide-Promoted Cyclizations of α-Amino Radicals Derived from α-Benzotriazolylalkenylamines

Journal of Organic Chemistry

Volumn 62, Issue 4, 1997, Pages 1125-1135

  Aurrecoechea, José M ^a   Lopez, Beatriz ^a   Fernández, Alvaro ^a   Arrieta, Ana ^a   Cossío, Fernando P ^a  

^a UNIVERSITY OF THE BASQUE COUNTRY UPV EHU   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001677592     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960957d     Document Type: Article

References (116)

1. Recent reviews: (a) Molander, G. A. Chem. Rev. 1992, 92, 29. (b) Molander, G. A. In Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons Inc: New York, 1994; Vol. 46, pp 211-367. (c) Imamoto, T. Lanthanides in Organic Synthesis; Academic Press: London, 1994. (d) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
2. Recent reviews: (a) Molander, G. A. Chem. Rev. 1992, 92, 29. (b) Molander, G. A. In Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons Inc: New York, 1994; Vol. 46, pp 211-367. (c) Imamoto, T. Lanthanides in Organic Synthesis; Academic Press: London, 1994. (d) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
3. Recent reviews: (a) Molander, G. A. Chem. Rev. 1992, 92, 29. (b) Molander, G. A. In Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons Inc: New York, 1994; Vol. 46, pp 211-367. (c) Imamoto, T. Lanthanides in Organic Synthesis; Academic Press: London, 1994. (d) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
4. Recent reviews: (a) Molander, G. A. Chem. Rev. 1992, 92, 29. (b) Molander, G. A. In Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons Inc: New York, 1994; Vol. 46, pp 211-367. (c) Imamoto, T. Lanthanides in Organic Synthesis; Academic Press: London, 1994. (d) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
5. Fernández-Acebes, A. Doctoral Thesis, Universidad del País Vasco, 1995.
6. (a) Imamoto, T.; Nishimura, S. Chem. Lett. 1990, 1141.
7. (b) Enholm, E. J.; Forbes, D. C.; Holub, D. P. Synth. Commun. 1990, 20, 981.
8. Souppe, J.; Danon, L.; Namy, J. L.; Kagan, H. B. J. Organomet. Chem. 1983, 250, 227.
9. Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y.; Ishii, Y. J. Org. Chem. 1994, 59, 7902.
10. (a) Sturino, C. F.; Fallis, A. G. J. Am. Chem. Soc. 1994, 116, 7447.
11. (b) Sturino, C. F.; Fallis, A. G. J. Org. Chem. 1994, 59, 6514.
12. Chiara, J. L.; Marco-Contelles, J.; Khiar, N.; Gallego, P.; Destabel, C.; Bernabé, M. J. Org. Chem. 1995, 60, 6010.
13. (a) Bowman, W. R.; Stephenson, P. T.; Young, A. R. Tetrahedron Lett. 1995, 36, 5623.
14. (b) Bowman, W. R.; Stephenson, P. T.; Terrett, N. K.; Young, A. R. Tetrahedron 1995, 51, 7959.
15. (a) Booth, S. E.; Jenkins, P. R.; Swain, C. J.; Sweeney, J. B. J. Chem. Soc., Perkin Trans. 1 1994, 3499.
16. (b) Keck, G. E.; McHardy, S. F.; Murry, J. A. J. Am. Chem. Soc. 1995, 117, 7289.
17. Marco-Contelles, J.; Destabel, C.; Gallego, P.; Chiara, J. L.; Bernabe, M. J. Org. Chem. 1996, 61, 1354, and references cited therein.
18. Kim, S.; Cheong, J. H.; Yoon, K. S. Tetrahedron Lett. 1995, 36, 6069.
19. Iminium cations are, on the other hand, reduced to the corresponding amines by the hydride reagent and are of no use in this methodology. See ref 8b.
20. Review on α-amino radicals: Renaud, P.; Giraud, L. Synthesis 1996, 913.
21. Martin, S. F.; Yang, C. P.; Laswell, W. L.; Rüeger, H. Tetrahedron Lett. 1988, 29, 6685.
22. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
23. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
24. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
25. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
26. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
27. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
28. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
29. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
30. Alternative methods for the generation and synthetic use of α-amino radicals: Radical translocation, (a) Murakami, M.; Hayashi, M.; Ito, Y. J. Org. Chem. 1992, 57, 793. (b) Williams, L.; Booth, S. E.; Undheim, K. Tetrahedron 1994, 50, 13697. Booth, S. E.; Benneche, T.; Undheim, K. Tetrahedron 1995, 51, 3665. Decarbonylation of α-amino acid chlorides, (d) Collin, J.; Namy, J. L.; Jones, G.; Kagan, H. B. Tetrahedron Lett. 1992, 33, 2973. Photoinduced electron transfer on amines, (e) Santamaria, J. Pure Appl. Chem. 1995, 67, 141. (f) Das, S.; Kumar, J. S. D.; Shivaramayya, K.; George, M. V. J. Chem. Soc., Perkin Trans. 1 1995, 1797. (g) Khim, S. K.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 999. (h) Hoegy, S. E.; Mariano, P. S. Tetrahedron Lett. 1994, 35, 8319. (i) Yoon, U. C.; Mariano, P. S. Acc. Chem. Res. 1992, 25, 233.
31. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
32. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
33. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
34. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
35. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
36. General references for the preparation and uses of iminium cations: (a) Paukstelis, J. V.; Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; pp 275-346. (b) Kleinman, E. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 893-951. (c) Overman, L. E.; Ricca, D. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1007-1046. (d) Hiemstra, H.; Speckamp, W. N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, pp 1047-1082. See also: (e) ref 14e. (f) Pandey, G. Synlett 1992, 546. (g) Risch, N.; Arend, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2422, and references therein.
37. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
38. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
39. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
40. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
41. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
42. Some recent references on cycloalkylamine natural products: (a) Jenkins, G. N.; Turner, N. J. Chem. Soc. Rev. 1995, 24, 169. (b) Kobayashi, Y.; Shiozaki, M. J. Org. Chem. 1995, 60, 2570. (c) Reference 7. (d) Isono, N.; Mori, M. J. Org. Chem. 1995, 60, 115. (e) Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T.; Hiramatsu, H. Tetrahedron Lett. 1995, 36, 253. (f) Trost, B. M.; Vanvranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
43. Katritzky, A. R.; Yannakapoulou, K.; Kuzmierkiewicz, W.; Aurrecoechea, J. M.; Palenik, G. J.; Koziol, A. E.; Szczesniak, M.; Skarjune, R. J. Chem. Soc., Perkin Trans. 1 1987, 2673.
44. Reviews: (a) Katritzky, A. R.; Lan, X. F.; Fan, W. Q. Synthesis 1994, 445. (b) Katritzky, A. R.; Rachwal, S.; Hitchings, G. J. Tetrahedron 1991, 47, 2683.
45. Reviews: (a) Katritzky, A. R.; Lan, X. F.; Fan, W. Q. Synthesis 1994, 445. (b) Katritzky, A. R.; Rachwal, S.; Hitchings, G. J. Tetrahedron 1991, 47, 2683.
46. (a) Aurrecoechea, J. M.; Fernández-Acebes, A. Synlett 1996, 39.
47. (b) Aurrecoechea, J. M.; Fernández-Acebes, A. Tetrahedron Lett. 1993, 34, 549.
48. Aurrecoechea, J. M.; Fernández-Acebes, A. Tetrahedron Lett. 1992, 33, 4763.
49. (a) Choi, J. K.; Ha, D. C.; Hart, D. J.; Lee, C. S.; Ramesh, S.; Wu, S. J. Org. Chem. 1989, 54, 279.
50. (b) Kano, S.; Yuasa, Y.; Asami, K.; Shibuya, S. Chem. Lett. 1986, 735.
51. Padwa, A.; Dent, W.; Nimmesgern, H.; Venkatramanan, M. K.; Wong, G. S. K. Chem. Ber. 1986, 119, 813.
52. Padwa, A.; Nimmesgern, H.; Wong, G. S. K. J. Org. Chem. 1985, 50, 5620.
53. (a) Takacs, J. M.; Helle, M. A.; Seely, F. L. Tetrahedron Lett. 1986, 27, 1257.
54. (b) Takacs, J. M.; Myoung, Y. C.; Anderson, L. G. J. Org. Chem. 1994, 59, 6928.
55. (a) Katritzky, A. R.; Yannakopoulou, K. Synthesis 1989, 747.
56. (b) Katritzky, A. R.; Long, Q. H.; Lue, P.; Jozwiak, A. Tetrahedron 1990, 46, 8153.
57. Simple α-benzotriazolylalkylamines decompose in contact with water and traces of acid or silica gel chromatography, reverting to the starting aldehyde and amine: Katritzky, A. R.; Yannakopoulou, K.; Lue, P.; Rasala, D.; Urogdi, L. J. Chem. Soc., Perkin Trans. 1 1989, 225.
58. Adducts 15-20 derived from aliphatic aldehydes 7-9 exist as 1/1 mixtures of the corresponding benzotriazol-1- and -2-yl isomers whereas in adducts 21, derived from aromatic aldehydes 10, the 1-isomer markedly predominates.
59. 13C NMR and MS for selected cases is also included in the supporting information.
60. 13C) and GC-MS data clearly support the proposed structures.
61. Molander, G. A.; Mckie, J. A. J. Org. Chem. 1993, 58, 7216.
62. (a) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J. Synlett 1992, 943.
63. (b) Curran, D. P.; Totleben, M. J. J. Am. Chem. Soc. 1992, 114, 6050.
64. (a) Udding, J. H.; Tuijp, C. J. M.; Hiemstra, H.; Speckamp, W. N. Tetrahedron 1994, 50, 1907.
65. (b) Esch, P. M.; Hiemstra, H.; de Boer, R. F.; Speckamp, W. N. Tetrahedron 1992, 48, 4659.
66. The presence of Sm(III), a Lewis acid, might facilitate an expectedly slow dissociation at temperatures below 25 °C. See: Katritzky, A. R.; Gordeev, M. F. J. Org. Chem. 1993, 58, 4049.
67. (a) Kocienski, P. J. Protecting Groups; Thieme: Stuttgart, 1994; p 220.
68. (b) Hormuth, S.; Reissig, H. U. J. Org. Chem. 1994, 59, 67.
69. (a) Lemaire-Audoire, S.; Savignac, M.; Genet, J. P.; Bernard, J. M. Tetrahedron Lett. 1995, 36, 1267.
70. (b) Talukdar, S.; Banerji, A. Synth. Commun. 1995, 25, 813.
71. Ito, H.; Taguchi, T.; Hanzawa,Y. J. Org. Chem. 1993, 58, 774.
72. Garrohelion, F.; Merzouk, A.; Guibe, F. J. Org. Chem. 1993, 58, 6109.
73. (e) Laguzza, B. C.; Ganem, B. Tetrahedron Lett. 1981, 22, 1483.
74. Bunce, R. A. Tetrahedron 1995, 51, 13103.
75. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
76. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
77. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
78. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
79. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
80. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
81. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
82. 2-mediated reactions have been reported: (a) Curran, D. P.; Wolin, R. L. Synlett 1991, 317. (b) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 313. (c) Enholm, E. J.; Jiang, S. Heterocycles 1992, 34, 2247. (d) Enholm, E. J.; Jiang, S. Tetrahedron Lett. 1992, 33, 6069. (e) Enholm, E. J.; Jiang, S. J.; Abboud, K. J. Org. Chem. 1993, 58, 4061. (f) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35, 1627. (g) Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori, N. Synth. Commun. 1995, 25, 389. (h) Enholm, E. J.; Schreier, J. A. J. Org. Chem. 1995, 60, 1110.
83. The hex-5-enyl radical numbering will be used throughout the discussion.
84. Examples of related radical translocations in amine derivatives: (a) Denenmark, D.; Hoffmann, P.; Winkler, T.; Waldner, A.; De Mesmaeker, A. Synlett 1991, 621. (b) Curran, D. P.; Liu, H. T. J. Chem. Soc., Perkin Trans. 1 1994, 1377. (c) Sato, T.; Kugo, Y.; Nakaumi, E.; Ishibashi, H.; Ikeda, M. J. Chem. Soc., Perkin Trans, 1 1995, 1801. See also refs 14a-c.
85. Examples of related radical translocations in amine derivatives: (a) Denenmark, D.; Hoffmann, P.; Winkler, T.; Waldner, A.; De Mesmaeker, A. Synlett 1991, 621. (b) Curran, D. P.; Liu, H. T. J. Chem. Soc., Perkin Trans. 1 1994, 1377. (c) Sato, T.; Kugo, Y.; Nakaumi, E.; Ishibashi, H.; Ikeda, M. J. Chem. Soc., Perkin Trans, 1 1995, 1801. See also refs 14a-c.
86. Examples of related radical translocations in amine derivatives: (a) Denenmark, D.; Hoffmann, P.; Winkler, T.; Waldner, A.; De Mesmaeker, A. Synlett 1991, 621. (b) Curran, D. P.; Liu, H. T. J. Chem. Soc., Perkin Trans. 1 1994, 1377. (c) Sato, T.; Kugo, Y.; Nakaumi, E.; Ishibashi, H.; Ikeda, M. J. Chem. Soc., Perkin Trans, 1 1995, 1801. See also refs 14a-c.
87. Cook, A. G. In Enamines. Synthesis, Structure and Reactions, 2nd ed.; Cook, A. G., Ed.; Marcel Dekker: New York, 1988; p 347.
88. 2. See: Angle, S. R.; Rainier, J. D. J. Org. Chem. 1992, 57, 6883.
89. Yu, Y. P.; Lin, R. H.; Zhang, Y. M. Tetrahedron Lett. 1993, 34, 4547.
90. See ref 38 for related observations.
91. Whitesell, J. K.; Minton, M. A. Stereochemical Analysis of Alycyclic Compounds by C-13 NMR Spectroscopy; Chapman and Hall: London, 1987.
92. Yadav, V.; Fallis, A. G. Can. J. Chem. 1991, 69, 779.
93. (a) Beckwith, A. L. J.; Schiesser, C. H. Tetrahedron 1985, 41, 3925.
94. (b) Spellmeyer, D. C.; Houk, K. M. J. Org. Chem. 1987, 52, 959.
95. Beckwith, A. L. J.; Zimmermann, J. J. Org. Chem. 1991, 56, 5791.
96. Beckwith, A. L. J. Chem. Soc. Rev. 1993, 22, 143.
97. (a) Bertrand, M. P.; De Riggi, I.; Lesueur, C.; Gastaldi, S.; Nouguier, R.; Jaime, C.; Virgili, A. J. Org. Chem. 1995, 60, 6040.
98. (b) Feldman, K. S.; Romanelli, A. L.; Ruckle, R. E.; Jean, G. J. Org. Chem. 1992, 57, 100.
99. Beckwith, A. L. J.; Easton, C. J.; Lawrence, T.; Serelis, A. K. Aust. J. Chem. 1983, 36, 545.
100. RajanBabu, T. V. Acc. Chem. Res. 1991, 24, 139.
101. The importance of a favorable polarization in the transition state on the rates of radical cyclization and radical hydrogen abstraction processes has been stressed: (a) Johnson, C. C.; Horner, J. H.; Tronche, C.; Newcomb, M. J. Am. Chem. Soc. 1995, 117, 1684. (b) Newcomb, M.; Horner, J. H.; Filipkowski, M. A.; Ha, C.; Park, S.-U. J. Am. Chem. Soc. 1995, 117, 3674. (c) Horner, J. H.; Martinez, F. N.; Musa, O. M.; Newcomb, M.; Shahin, H. E. J. Am. Chem. Soc. 1995, 117, 11124.
102. The importance of a favorable polarization in the transition state on the rates of radical cyclization and radical hydrogen abstraction processes has been stressed: (a) Johnson, C. C.; Horner, J. H.; Tronche, C.; Newcomb, M. J. Am. Chem. Soc. 1995, 117, 1684. (b) Newcomb, M.; Horner, J. H.; Filipkowski, M. A.; Ha, C.; Park, S.-U. J. Am. Chem. Soc. 1995, 117, 3674. (c) Horner, J. H.; Martinez, F. N.; Musa, O. M.; Newcomb, M.; Shahin, H. E. J. Am. Chem. Soc. 1995, 117, 11124.
103. The importance of a favorable polarization in the transition state on the rates of radical cyclization and radical hydrogen abstraction processes has been stressed: (a) Johnson, C. C.; Horner, J. H.; Tronche, C.; Newcomb, M. J. Am. Chem. Soc. 1995, 117, 1684. (b) Newcomb, M.; Horner, J. H.; Filipkowski, M. A.; Ha, C.; Park, S.-U. J. Am. Chem. Soc. 1995, 117, 3674. (c) Horner, J. H.; Martinez, F. N.; Musa, O. M.; Newcomb, M.; Shahin, H. E. J. Am. Chem. Soc. 1995, 117, 11124.
104. Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; p 149.
105. Stewart, J. J. P. J. Comput. Chem. 1989, 10, 209.
106. (a) Longuett-Higgins, H. C.; Pople, J. A. Proc. Phys. Soc. A68 1955, 591.
107. (b) Dewar, M. J. S.; Trinajstic, N. J. Chem. Soc. A 1971, 1220.
108. (a) Armstrong, D. A.; Rauk, A.; Yu, D. K. J. Am. Chem. Soc. 1993, 115, 666.
109. (b) Schubert, S.; Renaud, P.; Carrupt, P. A.; Schenk, K. Helv. Chim. Acta 1993, 76, 2473.
110. See reference 44b for related unfavorable secondary orbital interactions between the SOMO of an alkoxy-substituted radical and the HOMO of an electron-rich olefin that have been similarly used to explain a trans-preference in radical cyclizations. We thank the Editor for calling this work to our attention.
111. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.
112. (a) Bartels, R. H. Report CNA-44; University of Texas; Center for Numerical Analysis: Austin TX, 1972.
113. (b) Baker, J. J. Comput. Chem. 1986, 7, 385.
114. McIver, J. W.; Komornicki, A. K. J. Am. Chem. Soc. 1972, 94, 2625.
115. Gaussian 94, Revision B.2, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Pittsburgh PA, 1995.
116. Work is now in progress to extend these ab initio calculations to the rest of the TSs included in Chart 2 and to related systems.