Efficient intramolecular hydroamination of unactivated alkenes catalysed by butyllithium

European Journal of Organic Chemistry

Volumn , Issue 9, 2003, Pages 1623-1626

  Ates, Ali ^a   Quinet, Coralie ^a  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

Author keywords

Alkenes; Amination; Cyclization; Lithium

Indexed keywords

1 AMINO 2,2 DIMETHYLPENT 4 ENE; ALKENE DERIVATIVE; AMINE; BUTYLLITHIUM; LITHIUM DERIVATIVE; TETRAHYDROFURAN; UNCLASSIFIED DRUG;

AMINATION; ARTICLE; CATALYST; CHEMICAL BOND; CYCLIZATION; GAS CHROMATOGRAPHY; ISOMERISM; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; TEMPERATURE;

EID: 0037652138     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200300058     Document Type: Article

References (53)

1. General references: [1a] J. Seayad, A. Tillack, C. G. Hartung, M. Beller, Adv. Synth. Catal. 2002, 8, 344.
2. [1b] A. Togni, H. Grutzmacher, Catalytic Heterofunctionalization 2001, 91, Wiley-VCH Verlag GmbH.
3. [1c] T. E. Müller, M. Beller, Chem. Rev. 1998, 98, 675.
4. [1d] R. Taube Applied Homogenous Catalysis with Organometallic Compounds (Eds.: B. Cornils, W. A. Herrmann), Wiley-VCH: Weinheim, 1996, 1, 507.
5. [1e] D. M. Roundhill, Chem. Rev. 1992, 92, 1.
6. [1f] M. B. Gasc, A. Lattes, J. J. Perie, Tetrahedron 1983, 39, 703.
7. Intermolecular hydroamination of unactivated alkenes (alkali metals): [2a] W. Howk, E. L. Little, S. L, Scott, G. M, Whitman, J. Am. Chem. Soc. 1954, 76, 1899. [2b] R. D. Closson, J. P. Napolitano, G. G. Ecke, A. J. Kolka, J. Org. Chem. 1957, 22, 646. [2c] H. Lehmkuhl, D. Reinehr, J. Organomet. Chem. 1973, 55, 215. [2d] R. D. Closson, J. Wollensak, Organic Syntheses, collect. 1973, 5, 575, Wiley, NY. [2e] G. P. Pez, J. E. Galle, Pure Appl. Chem. 1985, 57, 1917.
8. Intermolecular hydroamination of unactivated alkenes (alkali metals): [2a] W. Howk, E, L. Little, S. L, Scott, G. M, Whitman, J. Am. Chem. Soc. 1954, 76, 1899. [2b] R. D. Closson, J. P. Napolitano, G. G. Ecke, A. J. Kolka, J. Org. Chem. 1957, 22, 646. [2c] H. Lehmkuhl, D. Reinehr, J. Organomet. Chem. 1973, 55, 215. [2d] R. D. Closson, J. Wollensak, Organic Syntheses, collect. 1973, 5, 575, Wiley, NY. [2e] G. P. Pez, J. E. Galle, Pure Appl. Chem. 1985, 57, 1917.
9. Intermolecular hydroamination of unactivated alkenes (alkali metals): [2a] W. Howk, E, L. Little, S. L, Scott, G. M, Whitman, J. Am. Chem. Soc. 1954, 76, 1899. [2b] R. D. Closson, J. P. Napolitano, G. G. Ecke, A. J. Kolka, J. Org. Chem. 1957, 22, 646. [2c] H. Lehmkuhl, D. Reinehr, J. Organomet. Chem. 1973, 55, 215. [2d] R. D. Closson, J. Wollensak, Organic Syntheses, collect. 1973, 5, 575, Wiley, NY. [2e] G. P. Pez, J. E. Galle, Pure Appl. Chem. 1985, 57, 1917.
10. Intermolecular hydroamination of unactivated alkenes (alkali metals): [2a] W. Howk, E, L. Little, S. L, Scott, G. M, Whitman, J. Am. Chem. Soc. 1954, 76, 1899. [2b] R. D. Closson, J. P. Napolitano, G. G. Ecke, A. J. Kolka, J. Org. Chem. 1957, 22, 646. [2c] H. Lehmkuhl, D. Reinehr, J. Organomet. Chem. 1973, 55, 215. [2d] R. D. Closson, J. Wollensak, Organic Syntheses, collect. 1973, 5, 575, Wiley, NY. [2e] G. P. Pez, J. E. Galle, Pure Appl. Chem. 1985, 57, 1917.
11. Intermolecular hydroamination of unactivated alkenes (alkali metals): [2a] W. Howk, E, L. Little, S. L, Scott, G. M, Whitman, J. Am. Chem. Soc. 1954, 76, 1899. [2b] R. D. Closson, J. P. Napolitano, G. G. Ecke, A. J. Kolka, J. Org. Chem. 1957, 22, 646. [2c] H. Lehmkuhl, D. Reinehr, J. Organomet. Chem. 1973, 55, 215. [2d] R. D. Closson, J. Wollensak, Organic Syntheses, collect. 1973, 5, 575, Wiley, NY. [2e] G. P. Pez, J. E. Galle, Pure Appl. Chem. 1985, 57, 1917.
12. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
13. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
14. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
15. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
16. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
17. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
18. Intermolecular hydroamination of unactivated alkenes (transition metals): [3a] D. R. Coulson, Tetrahedron. Lett. 1971, 12, 429 [3b] B. Akermark, J. E. Bäckvall, K. Siirala-Hansen, K. Sjöberg, K. Zetterberg, L. S. Hegedus, J. Organomet. Chem. 1974, 72, 127. [3c] A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738. [3d] J.-J. Brunet, D. Neibecker, K. Philippot, Tetrahedron. Lett. 1993, 34, 3877. [3e] J.-J. Brunet, G. Commenges, D. Neibecker, K. Philippot, J. Organomet. Chem. 1994, 469, 221. [3f] R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857. [3g] R. Q. Su, T. Müller, Tetrahedron 2001, 57, 6027.
19. Intramolecular hydroamination of unactivated alkenes (transition metals): [4a] J. Ambühl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, Angew. Chem. Int. Ed. Engl. 1975, 14, 369. [4b] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Ughetto, L. Zambonelli, J. Organomet. Chem. 1978, 160, 329. [4c] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, J. Organomet. Chem. 1979, 181, 255.
20. Intramolecular hydroamination of unactivated alkenes (transition metals): [4a] J. Ambühl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, Angew. Chem. Int. Ed. Engl. 1975, 14, 369. [4b] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Ughetto, L. Zambonelli, J. Organomet. Chem. 1978, 160, 329. [4c] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, J. Organomet. Chem. 1979, 181, 255.
21. Intramolecular hydroamination of unactivated alkenes (transition metals): [4a] J. Ambühl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, Angew. Chem. Int. Ed. Engl. 1975, 14, 369. [4b] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Ughetto, L. Zambonelli, J. Organomet. Chem. 1978, 160, 329. [4c] J. Ambuehl, P. S. Pregosin, L. M. Venanzi, G. Consiglio, F. Bachechi, L. Zambonelli, J. Organomet. Chem. 1979, 181, 255.
22. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
23. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
24. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
25. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
26. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
27. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
28. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
29. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
30. Intramolecular hydroamination of unactivated alkenes (lanthanides): [5a] M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108. [5b] M. R. Gagné, S. P. Nolan, T. J. Marks, Organometallics 1990, 9, 1716. [5c] M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003. [5d] M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275. [5e] G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983. [5f] J.-S. Ryu, T. J. Marks, F. E. McDonald, Org. Lett. 2001, 3, 3091. [5f] G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344. [5h] S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886. [5i] Y. K. Kim, T. Livinghouse, Angew. Chem. Int. Ed. 2002, 41, 3645.
31. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
32. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
33. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
34. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
35. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
36. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
37. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
38. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
39. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
40. Intermolecular hydroamination of Styrene and derivatives (alkali metals): [6a] R. Wegler, G. Pieper, Chem. Ber. 1950, 83, 1. [6b] T. Asahara, M. Seno, S. Tanabe, N. Den, Bull. Chem. Soc. Jpn. 1969, 42, 1996. [6c] R. J. Schlott, J. C. Falk, K. W. Narducy, J. Org. Chem. 1972, 37, 4243. [6d] T. Narita, T. Yamaguchi, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 3825. [6e] H. Fujita, M. Tokuda, M. Nitta, H. Suginome, Tetrahedron Lett. 1992, 33, 6359. [6f] M. Beller, C. Breindl, T. H. Riemeier, M. Eichberger, H. Trauthwein, Angew. Chem. 1998, 110, 3575; Angew. Chem. Int. Ed. 1998, 37, 3389. [6g] J. A. Seijas, M. P. Vaquez-Tato, C. Entenza, M. M. Martinez, M. G. Onega, S. Veiga, Tetrahedron. Lett. 1998, 39, 5073. [6h] M. Beller, C. Breindl, Tetrahedron 1998, 54, 6359. [6i] C. G. Hartung, C. Breindl, A. Tillack, M. Beller, Tetrahedron 2000, 56, 5157.
41. Intermolecular hydroamination of styrene and derivatives (transition metals): [7a] M. Beller, M. Eichberger, H. Trautwein, Angew. Chem. Int. Ed. Engl. 1997, 36, 2225. [7b] M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Müller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306. [7c] M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546. [7d] M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett 2002, 10, 1579. [7e] U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166.
42. Intermolecular hydroamination of styrene and derivatives (transition metals): [7a] M. Beller, M. Eichberger, H. Trautwein, Angew. Chem. Int. Ed. Engl. 1997, 36, 2225. [7b] M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Müller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306. [7c] M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546. [7d] M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett 2002, 10, 1579. [7e] U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166.
43. Intermolecular hydroamination of styrene and derivatives (transition metals): [7a] M. Beller, M. Eichberger, H. Trautwein, Angew. Chem. Int. Ed. Engl. 1997, 36, 2225. [7b] M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Müller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306. [7c] M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546. [7d] M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett 2002, 10, 1579. [7e] U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166.
44. Intermolecular hydroamination of styrene and derivatives (transition metals): [7a] M. Beller, M. Eichberger, H. Trautwein, Angew. Chem. Int. Ed. Engl. 1997, 36, 2225. [7b] M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Müller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306. [7c] M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546. [7d] M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett 2002, 10, 1579. [7e] U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166.
45. Intermolecular hydroamination of styrene and derivatives (transition metals): [7a] M. Beller, M. Eichberger, H. Trautwein, Angew. Chem. Int. Ed. Engl. 1997, 36, 2225. [7b] M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Müller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306. [7c] M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546. [7d] M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett 2002, 10, 1579. [7e] U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166.
46. Intermolecular hydroamination of 1,3-dienes (alkali metals): [8a] N. Imai, T. Narita, T. Tsuruta, Tetrahedron Lett. 1971, 38, 3517. [8b] T. Narita, N. Imai, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 1242. [8c] T. Fujita, K. Suga, S. Watanabe, Aust. J. Chem. 1974, 27, 531.
47. Intermolecular hydroamination of 1,3-dienes (alkali metals): [8a] N. Imai, T. Narita, T. Tsuruta, Tetrahedron Lett. 1971, 38, 3517. [8b] T. Narita, N. Imai, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 1242. [8c] T. Fujita, K. Suga, S. Watanabe, Aust. J. Chem. 1974, 27, 531.
48. Intermolecular hydroamination of 1,3-dienes (alkali metals): [8a] N. Imai, T. Narita, T. Tsuruta, Tetrahedron Lett. 1971, 38, 3517. [8b] T. Narita, N. Imai, T. Tsuruta, Bull. Chem. Soc. Jpn. 1973, 46, 1242. [8c] T. Fujita, K. Suga, S. Watanabe, Aust. J. Chem. 1974, 27, 531.
49. Intermolecular hydroamination of 1,3-dienes (transition metals): [9a] O. Löber, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2001, 123, 4366. [9b] J. Pawlas, Y. Nakao, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 3669 and references cited herein.
50. Intermolecular hydroamination of 1,3-dienes (transition metals): [9a] O. Löber, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2001, 123, 4366. [9b] J. Pawlas, Y. Nakao, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 3669 and references cited herein.
51. In many cases, the sodium-potassium amalgam leaves the substrate intact and rigorously dry after vacuum transfer. In some cases, although the same substrate and the same conditions were used, the hydroamination as well as the isomerisation of the double bond was observed during this drying step. Traces of impurities in the metallic sources could be the cause of these observations.
52. To the best of our knowledge, no report of simple and efficient intramolecular hydroamination reactions of unactivated alkenes with alkali-metal catalysts has been published in the literature so far.
53. When this reaction was performed at room temperature, the ratio of cyclised and isomerised products 8:9 was 25:75 after more than 65% conversion.