Rhodium-catalyzed reaction of N-(2-pyridinyl)piperazines with CO and ethylene. A novel carbonylation at a C-H bond in the piperazine ring

Organometallics

Volumn 16, Issue 16, 1997, Pages 3615-3622

  Ishii, Yutaka ^a   Chatani, Naoto ^a   Kakiuchi, Fumitoshi ^a   Murai, Shinji ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000789076     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970372p     Document Type: Article

References (46)

1. (a) Yoshimura, N.; Moritani, I.; Shimamura, T.; Murahashi, S.-I. J. Am. Chem. Soc. 1973, 95, 3038.
2. (b) Yoshimura, N.; Moritani, I.; Shimamura, T.; Murahashi, S.-I. J. Chem. Soc., Chem. Commun. 1973, 307.
3. (c) Murahashi, S.-I.; Yoshimura, N.; Tsumiyama, T.; Kojima, T. J. Am. Chem. Soc. 1983, 105, 5002.
4. De Angelis, F.; Grgurina, I.; Nicoletti, R. Synthesis 1979, 70.
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7. 12 in the presence of water: Shvo, Y.; Laine, R. M. J. Chem. Soc., Chem. Commun. 1980, 753.
8. For recent reviews on metal-catalyzed oxidations of amines and related reactions, see: Murahashi, S.-I. Angew. Chem., Int. Ed. Engl. 1995, 34, 2443. Murahashi, S.-I.; Naota, T. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 12, pp 1177-1192.
9. For recent reviews on metal-catalyzed oxidations of amines and related reactions, see: Murahashi, S.-I. Angew. Chem., Int. Ed. Engl. 1995, 34, 2443. Murahashi, S.-I.; Naota, T. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 12, pp 1177-1192.
10. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
11. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
12. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
13. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
14. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
15. The utility of a pyridine ring as a directing group for C-H bond cleavage has been described. (a) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Chem. Commun. 1994, 2267. (b) Lim, Y.-G.; Kim, Y. H.; Kang, J.-B. J. Chem. Soc., Perkin Trans. 1 1996, 2201. (c) Lim, Y.-G.; Kang, J.-B.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1996, 585. (d) Fujii, N.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem. Lett. 1996, 939. (e) Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Chem. Lett. 1997, 425. (f) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604.
16. The structure of 2a was confirmed by X-ray analysis.
17. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
18. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
19. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
20. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
21. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
22. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
23. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
24. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
25. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
26. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
27. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
28. For papers on transition-metal-catalyzed dehydrogenation of alkanes to alkenes under thermal conditions, see: Felkin, H.; Fillebeen-Khan, T.; Gault, Y.; Holmes-Smith, R.; Zakrzewski, J. Tetrahedron Lett. 1984, 25, 1279. Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Yingrui, L. Tetrahedron Lett. 1985, 26, 1999. Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. Maguire, J. A.; Petrillo, A.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 9492. Gupta, M.; Hagen, C.; Kaska, W. C.; Flesher, R.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1996, 2083. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840. Gupta, M.; Kaska, W. C.; Jensen, C. M. J. Chem. Soc., Chem. Commun. 1997, 461. Leitner, W.; Six, C. Chem. Ber. 1997, 130, 555. For papers on transition-metal-catalyzed dehydrogenation of alkanes by irradiation, see: Nomura, K.; Saito, Y. J. Chem. Soc., Chem. Commun. 1988, 161, Sakakura, T.; Sodeyama, T.; Tokunaga, M.; Tanaka, M. Chem. Lett. 1988, 263. Maguire, J. A.; Boese, W. T.; Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. Tanaka, M.; Sakakura, T. Pure Appl. Chem. 1990, 62, 1147 and references cited therein.
29. 11 reported the Rh-catalyzed transfer of hydrogen from 1,4-dioxane to alkene leading to dioxene and alkane.
30. Nishiguchi, T.; Tachi, K.; Fukuzumi, K. J. Am. Chem. Soc. 1972, 94, 8916. Nishiguchi, T.; Fukuzumi, K. J. Am. Chem. Soc. 1974, 96, 1893.
31. Nishiguchi, T.; Tachi, K.; Fukuzumi, K. J. Am. Chem. Soc. 1972, 94, 8916. Nishiguchi, T.; Fukuzumi, K. J. Am. Chem. Soc. 1974, 96, 1893.
32. Masters, C.; Kiffen, A. A.; Visser, J. P. J. Am. Chem. Soc. 1976, 98, 1357. 1,4-Dimethylpiperazine was also used as a hydrogen donor in place of dioxane, albeit with low efficiency.
33. 2 C-H bond was reported: Moore, E.; Pretzer, W. R.; O'Connell, T. J.; Harris, J.; LaBounty, L.; Chou, L.; Grimmer, S. S. J. Am. Chem. Soc. 1992, 114, 5888. Chatani, N.; Fukuyama, T.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 1996, 118, 493. See also ref 6f.
34. 2 C-H bond was reported: Moore, E.; Pretzer, W. R.; O'Connell, T. J.; Harris, J.; LaBounty, L.; Chou, L.; Grimmer, S. S. J. Am. Chem. Soc. 1992, 114, 5888. Chatani, N.; Fukuyama, T.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 1996, 118, 493. See also ref 6f.
35. 6f
36. Monitoring by GC shows that most of the reactions described are completed within 20 h. Longer reaction time (40 h) did not increase the product yield. The GC monitoring indicates that the time-course yields and the final yields reflect the rate of the reaction.
37. 2 gave dehydrogenation products. Mitsudo, T.; Furukawa, T.; Ambe, M.; Fujita, K.; Yamamoto, J.; Kondo, T. 70th Annual Meeting of Japanese Chemical Society, Tokyo, 4J207, p 1311 (1996).
38. 6f and pyridinyl olefins: Chatani, N.; Ishii, Y.; Ie, Y.; Kakiuchi, F.; Murai, S. Unpublished data.
39. 3 C-H bonds, see: Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J. Am. Chem. Soc. 1990, 112, 7221.
40. For a paper on Pd(II)-induced dehydrogenation of β-amino ketones, see: Murahashi, S.-I.; Tsumiyama, T.; Mitsue, Y. Chem. Lett. 1984, 1419. Murahashi, S.-I.; Mitsue, Y.; Tsumiyama, T. Bull. Chem. Soc. Jpn. 1987, 60, 3285.
41. For a paper on Pd(II)-induced dehydrogenation of β-amino ketones, see: Murahashi, S.-I.; Tsumiyama, T.; Mitsue, Y. Chem. Lett. 1984, 1419. Murahashi, S.-I.; Mitsue, Y.; Tsumiyama, T. Bull. Chem. Soc. Jpn. 1987, 60, 3285.
42. Although the presence of a pyridine ring is not essential for the dehydrogenation step (1a → 16), it is clear that the pyridine ring is much more efficient for the dehydrogenation to take place than an aryl group.
43. 2 C-Rh bond.
44. Because 16 could not be detected by GC in the reaction mixture, an alternative path, which does not require the formation of olefin 16, via α-hydride elimination from 24, cannot be excluded. equation presented
45. Hassner, A.; Krepski, L. R.; Alexanian, V. Tetrahedron 1978, 34, 2069.
46. Moore, M. L. Org. React. 1949, 5, 323.