First [4 + 3] annulation of alkynyl Fischer carbene complexes and azadienes. X-ray structure of a metalated zwitterionic intermediate

Journal of the American Chemical Society

Volumn 118, Issue 3, 1996, Pages 695-696

  Barluenga, José ^a   Tomás, Miguel ^a   Rubio, Eduardo ^a   López Pelegrín, José A ^a   García Granda, Santiago ^a   Pertierra, Pilar ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000717018     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja952710o     Document Type: Article

References (74)

1. (a) Wulff W. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065.
2. (b) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587.
3. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
4. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
5. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
6. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
7. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
8. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
9. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
10. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
11. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
12. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
13. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
14. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
15. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
16. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
17. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
18. For nitrogen nucleophiles, see, for instance: (a) Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; de Meijere, A. Chem. Ber. 1994, 127, 911. (b) Stein, F.; Duetsch, M.; Pohl, E.; Herbst-Irmer, R.; de Meijere, A. Organometallics 1993, 12, 2556. (c) Pipoh, R.; van Eldik, R.; Henkel, G. Ibid. 1993, 12, 2236. (d) Pipoh, R.; van Eldik, R. Ibid. 1993, 12, 2668. (e) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. ibid. 1994, 13, 3502. (f) Rahm, A.; Wulff, W. D.; Rheingold, A. L. Ibid. 1993, 12, 597. (g) Duetsch, M.; Lackmann, R.; Stein, F.; de Meijere, A. Synlett 1991, 324. (h) Aumann, R. Chem. Ber. 1994, 127, 725. (i) Aumann, R.; Hinterding, P. Ibid. 1993, 126, 421. For oxygen nucleophiles, see: (j) Stein, F.; Duetsch, M.; Lackmann, R.; Noltemeyer, M.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1658. (k) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. J. Organomet. Chem. 1991, 401, C17. (l) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (m) Segundo, A.; Moretó, J. M.; Vinas, J. M.; Ricart, S.; Molins, E. Organometallics 1994, 13, 246. (n) Aumann, R. Chem. Ber. 1992, 125, 2773. For phosphorus nucleophiles, see: (o) Aumann, R.; Jasper, B.; Fröhlich, R. Organometallics 1995, 14, 231. For carbon nucleophiles, see: (p) Aumann, R.; Kosmeier, M.; Roths, K.; Fröhlich, R. Synlett 1994, 1041. For the ene reaction with electron-rich alkenes, see ref 3a.
19. (a) Faron, K. L.; Wulff, W. D. J. Am. Chem. Soc. 1990, 112, 6419.
20. (b) Faron, K. L.; Wulff, W. D. Ibid. 1988, 110, 8727.
21. (c) Aumann, R.; Roths, K.; Läge, M.; Krebs, B. Synlett 1993, 667.
22. (d) Pipoh, R.; van Eldik, R.; Wang, S. L. B.; Wulff, W. D. Organometallics 1992, 11, 490.
23. (e) Camps, F.; Moretó, J. M.; Ricart, S.; Viñas, J. M.; Molins, E.; Miravitlles, C. J. Chem. Soc., Chem. Commun. 1989, 1560.
24. (f) Camps, F.; Llebaria, A.; Moretó, J. M.; Ricart, S.; Viñas, J. M. Tetrahedron Lett. 1990, 31, 2479.
25. (a) Kreissl, F. R.; Fischer, E. O.; Kreiter, C. G. J. Organomet. Chem. 1973, 57, C9.
26. (b) Chan, K. S.; Wulff, W. D. J. Am. Chem. Soc. 1986, 108, 5229.
27. (c) Chan, K. S.; Yeung, M. L.; Chan, W.; Wang, R.; Mak, T. C. W. J. Org. Chem. 1995, 60, 1741.
28. (d) Chan, K. S. J. Chem. Soc., Perkin Trans. 1 1991, 2602.
29. (a) Wang, S. L. B.; Wulff, W. D. J. Am. Chem. Soc. 1990, 112, 4550.
30. (b) Merlic, C. A.; Xu, D. Ibid. 1991, 113, 9855.
31. (c) Aumann, R.; Roths, K.; Grehl, M. Synlett 1993, 669.
32. Reference 2p.
33. (a) Wulff, W. D.; Yang, D. C. J. Am. Chem. Soc. 1984, 106, 7565.
34. (b) Wulff, W. D.; Yang, D. C. Ibid. 1984, 106, 7656.
35. (c) Bao, J.; Dragisich, V.; Wenglowsky, S.; Wulff, W. D. Ibid. 1991, 113, 9873.
36. (d) Bao, J.; Wulff, W. D.; Dragisich, V.; Wenglowsky, S.; Ball, R. G. Ibid. 1994, 116, 7616.
37. (e) Wulff, W. D.; Tang, P. C.; Chan, K. S.; McCallum, J. S.; Yang, D. C.; Gilbertson, S. R. Tetrahedron 1985, 41, 5813.
38. (f) Barluenga, J.; Aznar, F.; Barluenga, S. J. Chem. Soc., Chem. Commun. 1995, 1973.
39. (a) Dötz, K. H.; Christoffers, J. J. Organomet. Chem. 1992, 426, C58.
40. (b) Camps, F.; Moretó, J. M.; Ricart, S.; Viñas, J. M. Angew. Chem. Int., Ed. Engl. 1991, 30, 1470.
41. (a) Wulff, W. D.; Yang, D. C.; Murray, C. K. J. Am. Chem. Soc. 1988, 110, 2653.
42. (b) Barluenga, J.; Aznar, F.; Martín, A.; García-Granda, S.; Salvadó, M. A.; Pertierra, P. J. Chem. Soc., Chem. Commun. 1993, 319.
43. (c) Barluenga, J.; Aznar, F.; Martín, A. Organometallics 1995, 14, 1429.
44. (d) Barluenga, J.; Aznar, F.; Valdés, C.; Martín, A.; García-Granda, S.; Martin, E. J. Am. Chem. Soc. 1993, 115, 4403.
45. (e) Harvey, D. F.; Grenzer, M. E.; Gantzel, P. K. Ibid. 1994, 116, 6719.
46. For cycloheptaallenic species, see: (a) Dolbier, W. R., Jr.; Garza, O. T.; Al-Sader, B. H. J. Am. Chem. Soc. 1975, 97, 5038. (b) Manisse, N.; Chuche, J. Ibid. 1977, 99, 1272. (c) Manisse, N.; Chuche, J. Tetrahedron 1977, 33, 2399. (d) Chapman, O. L.; Johnson, J. W.; McMahon, R. J.; West, P. R. J. Am. Chem. Soc. 1988, 110, 501.
47. For cycloheptaallenic species, see: (a) Dolbier, W. R., Jr.; Garza, O. T.; Al-Sader, B. H. J. Am. Chem. Soc. 1975, 97, 5038. (b) Manisse, N.; Chuche, J. Ibid. 1977, 99, 1272. (c) Manisse, N.; Chuche, J. Tetrahedron 1977, 33, 2399. (d) Chapman, O. L.; Johnson, J. W.; McMahon, R. J.; West, P. R. J. Am. Chem. Soc. 1988, 110, 501.
48. For cycloheptaallenic species, see: (a) Dolbier, W. R., Jr.; Garza, O. T.; Al-Sader, B. H. J. Am. Chem. Soc. 1975, 97, 5038. (b) Manisse, N.; Chuche, J. Ibid. 1977, 99, 1272. (c) Manisse, N.; Chuche, J. Tetrahedron 1977, 33, 2399. (d) Chapman, O. L.; Johnson, J. W.; McMahon, R. J.; West, P. R. J. Am. Chem. Soc. 1988, 110, 501.
49. For cycloheptaallenic species, see: (a) Dolbier, W. R., Jr.; Garza, O. T.; Al-Sader, B. H. J. Am. Chem. Soc. 1975, 97, 5038. (b) Manisse, N.; Chuche, J. Ibid. 1977, 99, 1272. (c) Manisse, N.; Chuche, J. Tetrahedron 1977, 33, 2399. (d) Chapman, O. L.; Johnson, J. W.; McMahon, R. J.; West, P. R. J. Am. Chem. Soc. 1988, 110, 501.
50. Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; López-Ortiz, F.; Carbajo, R. J.; García-Granda, S.; Pertierra, P. Chem.-Eur. J. 1996, 2, 180.
51. The 1,2-and 1,4-addition of amines (see refs 2b-i) and imines (see ref 2a) to alkynyl carbene complexes is well documented.
52. For previous work on Fischer carbene complexes and simple 1-azadienes, see: (a) Barluenga, J.; Tomás, M.; López Pelegrín, J. A.; Rubio, E. J. Chem. Soc., Chem. Commun. 1995, 665. (b) Danks, T. N.; Velo-Rego, D. Tetrahedron Lett. 1994, 35, 9443.
53. For previous work on Fischer carbene complexes and simple 1-azadienes, see: (a) Barluenga, J.; Tomás, M.; López Pelegrín, J. A.; Rubio, E. J. Chem. Soc., Chem. Commun. 1995, 665. (b) Danks, T. N.; Velo-Rego, D. Tetrahedron Lett. 1994, 35, 9443.
54. 3 = Ph) in THF at 20 °C resulted in the formation of 3a (55%) along with a second compound (28%) resulting from the [4 + 2] cycloaddition of the azadiene to the alkynyl function of the carbene complex. Unpublished results.
55. This metal migration has been independently invoked by Fischer and Dötz to rationalize the cyclodimerization of alkynyl carbenes of chromium and tungsten that occurs on reaction with organolithium and organozinc reagents. See: (a) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (b) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 123, 1799.
56. This metal migration has been independently invoked by Fischer and Dötz to rationalize the cyclodimerization of alkynyl carbenes of chromium and tungsten that occurs on reaction with organolithium and organozinc reagents. See: (a) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (b) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 123, 1799.
57. (a) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389.
58. (b) Sleiman, H. F.; McElwee-White, L. J. Am. Chem. Soc. 1988, 110, 8700.
59. (c) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. Ibid. 1992, 114, 5153.
60. (d) Hegedus, L. S.; Lundmark, B. R. Ibid. 1989, 111, 9194.
61. 2-tungsten-allene intermediates has been recently proposed: Chen, C. C.; Fan, J. S.; Lee, G. H.; Peng, S. M.; Wang, S. L.; Liu, R. S. J. Am. Chem. Soc. 1995, 117, 2933.
62. -1, T = 293 K. Colorless crystal (0.30 × 0.30 × 0.26 mm).
63. 6 did not lead to the deuterated azepinone 5, but 4b was the sole product detected.
64. 1-alkenyl chromium complex species is known: Herndon, J. W.; Reid, M. D. J. Am. Chem. Soc. 1994, 116, 383.
65. Reviews, on azepines: (a) Evans, P. A.; Holmes, A. B. Tetrahedron 1991, 47, 9131.
66. (b) Hassenrück, K.; Martin, H. D. Synthesis 1988, 569.
67. (c) Smalley, R. K. In Comprehensive Heterocyclic Chemistry; Lwowski, W., Ed.; Pergamon: Oxford, 1984; Vol. 7, p 491.
68. For recent syntheses of 2-azepinones, see: (d) Robl, J. A.; Cimarusti, M. P. Tetrahedron Lett. 1994, 35, 1393.
69. (e) Robl, J. A.; Cimarusti, M. P.; Simpkins, L. M.; Weller, H. N.; Pan, Y. Y.; Malley, M.; DiMarco, J. D. J. Am. Chem. Soc. 1994, 116, 2348.
70. (f) Evans, P. A.; Holmes, A. B.; Russell, K. J. Chem. Soc., Perkin Trans. 1 1994, 3397.
71. (g) Evans, P. A.; Holmes, A. B. Tetrahedron 1991, 47, 9131.
72. 22
73. The preference for the [4 + 2] cycloaddition of tungsten carbenes compared with chromium carbenes has been reported: (a) Wulff, W. D.; Bauta, W. E.; Kaesler, R. W.; Lankford, P. J.; Miller, R. A.; Murray, C. K.; Yang, D. C. J. Am. Chem. Soc. 1990, 112, 3642. (b) Barluenga, J.; Aznar, F.; Martín, A.; Barluenga, S.; García-Granda, S.; Paneque-Quevedo, A. A. J. Chem. Soc., Chem. Commun. 1994, 843.
74. The preference for the [4 + 2] cycloaddition of tungsten carbenes compared with chromium carbenes has been reported: (a) Wulff, W. D.; Bauta, W. E.; Kaesler, R. W.; Lankford, P. J.; Miller, R. A.; Murray, C. K.; Yang, D. C. J. Am. Chem. Soc. 1990, 112, 3642. (b) Barluenga, J.; Aznar, F.; Martín, A.; Barluenga, S.; García-Granda, S.; Paneque-Quevedo, A. A. J. Chem. Soc., Chem. Commun. 1994, 843.