Transition metal-catalyzed hetero-[5 + 2] cycloadditions of cyclopropyl imines and alkynes: Dihydroazepines from simple, readily available starting materials

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15154-15155

  Wender, Paul A ^a   Pedersen, Torben M ^a   Scanio, Marc J C ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; AZEPINE DERIVATIVE; CYCLOPROPANE DERIVATIVE; DIHYDROAZEPINE DERIVATIVE; IMINE; TRANSITION ELEMENT; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CYCLOADDITION; REACTION ANALYSIS; SYNTHESIS;

EID: 0037176267     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0285013     Document Type: Article

References (20)

1. For a general review, see: Wender, P. A.; Bi, F. C.; Gamber, G. G.; Gosselin, F.; Hubbard, R. D.; Scanio, M. J. C.; Sun, R.; Williams, T. J.; Zhang, L. Pure Appl. Chem. 2002. 74, 25-31.
2. For the initial examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977. [6 + 2] cycloadditions: (c) Wender, P. A.; Correa, A. G.; Sato, Y.: Sun, R. J. Am. Chem. Soc. 2000, 122. 7815-7816. [5 + 2 + 1] cycloadditions: (d) Wender, P. A.; Gamber G. G.; Hubbard, R. D.; Zhang, L. J. Am. Chem. Soc. 2002, 124, 2876-2877.
3. For the initial examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977. [6 + 2] cycloadditions: (c) Wender, P. A.; Correa, A. G.; Sato, Y.: Sun, R. J. Am. Chem. Soc. 2000, 122. 7815-7816. [5 + 2 + 1] cycloadditions: (d) Wender, P. A.; Gamber G. G.; Hubbard, R. D.; Zhang, L. J. Am. Chem. Soc. 2002, 124, 2876-2877.
4. For the initial examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977. [6 + 2] cycloadditions: (c) Wender, P. A.; Correa, A. G.; Sato, Y.: Sun, R. J. Am. Chem. Soc. 2000, 122. 7815-7816. [5 + 2 + 1] cycloadditions: (d) Wender, P. A.; Gamber G. G.; Hubbard, R. D.; Zhang, L. J. Am. Chem. Soc. 2002, 124, 2876-2877.
5. For the initial examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977. [6 + 2] cycloadditions: (c) Wender, P. A.; Correa, A. G.; Sato, Y.: Sun, R. J. Am. Chem. Soc. 2000, 122. 7815-7816. [5 + 2 + 1] cycloadditions: (d) Wender, P. A.; Gamber G. G.; Hubbard, R. D.; Zhang, L. J. Am. Chem. Soc. 2002, 124, 2876-2877.
6. For recent examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Zhang, L. Org. Lett. 2000, 2, 2323-2326. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Gamber, G. G.; Scanio, M. J. C. Angew. Chem., Int. Ed. 2001, 40, 3895-3897.
7. For recent examples, see the following. Intramolecular [5 + 2] cycloadditions: (a) Wender, P. A.; Zhang, L. Org. Lett. 2000, 2, 2323-2326. Intermolecular [5 + 2] cycloadditions: (b) Wender, P. A.; Gamber, G. G.; Scanio, M. J. C. Angew. Chem., Int. Ed. 2001, 40, 3895-3897.
8. For a review of azepine natural products, see: O'Hagan, D. Nat. Prod. Rep. 1997, 14, 637-651.
9. (a) Kamitani, A.; Chatani, N.; Morimoto, T.; Murai, S. J. Org. Chem. 2000, 65, 9230-9233.
10. For a review of carbonylative cycloadditions, see: (b) Khumtaveeporn, K.; Alper, H. Acc. Chem. Res. 1995, 28, 414-422.
11. Examples of heteroatom variants of the five-carbon VCP include vinylaziridines, vinyl epoxides, C-cyclopropyl imines, N-cyclopropyl imines, and cyclopropanecarboxaldehydes.
12. 4 was ineffective as a catalyst.
13. (a) Yamamoto, Y.; Takagishi, H.; Itoh, K. J. Am. Chem. Soc. 2002, 124, 6844-6845 and references therein.
14. (b) For a review of [2 + 2 + 2] cycloadditions, see: Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901-2915.
15. 2O, acetone) gave yields which were generally lower.
16. The current reaction conditions work best with acetylene diesters. Acetylene monoesters, phenyl acetylene, and propargyl alcohol derivatives were unreactive. Further studies on alkyne variations are in progress.
17. A previous attempt on use of N-cyclopropyl benzaldimine as substrate for a hetero-[5 + 2] cycloaddition was unsuccessful.
18. (a) Wender, P. A.; Dyckman, A. J.; Husfeld, C. O.; Kadereit, D.; Love, J. A.; Rieck, H. J. Am. Chem. Soc. 1999, 121, 10442-10443.
19. (b) Wender, P. A.; Dyckman, A. J. Org. Lett. 1999, 1, 2089-2092.
20. The regiochemical outcome was determined by decoupling NMR experiments detailed in the Supporting Information.