Diastereoselective formation of 5-vinylcyclopentenes from 1,6-enynes: Cobalt-mediated C-H allylic activation and formal 5-endo-dig cyclization

Organic Letters

Volumn 2, Issue 12, 2000, Pages 1753-1756

  Dolaine, Régis ^a   Gleason, James L ^a  

^a MCGILL UNIVERSITY   (Canada)

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Indexed keywords

EID: 0004456781     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol005928a     Document Type: Article

References (30)

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21. (e) For comparison of various stoichiometric protocols, see ref 3d.
22. See ref 1b and (a) Pagenkopf, B. L.; Livinahouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
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24. 8 (632 mg, 1.85 mmol. 1.20 equiv) is added to a solution of the eneyne 1a (500 mg. 1.54 mmol, 1.00 equiv) in anhydrous toluene (40 mL). After stirring at 21°C for 2 h, the black solution is heated at reflux for 12 h, during which time a suspension forms and a cobalt(0) mirror coating is observed on the sides of the flask. After cooling to 21°C, the black suspension is concentrated, and the products are separated using chemical derivatization and flash chromatography techniques. For full details see Supporting Information.
25. LaBelle, B. E.; Knudsen, M. J.; Olmstead, M. M.; Hope, H.; Yanuckz, M. D.; Schore, N. E. J. Org. Chem. 1985, 50, 5215.
26. This reaction appears to be mechanistically different from the interrupted Pauson-Khand reaction reported by Krafft. See: Krafft, M. E.; Wilson, A. M.; Dasse, O. A.; Shao, B.; Cheung, Y. Y.; Fu, Z.; Bonaga, L. V. R.; Mollman, M. K. J. Am. Chem. Soc. 1996, 118. 6080.
27. As with the Pauson-Khand reaction, it has not been possible to detect any intermediates other than the initial cobalt complex 5. Evidence for the initial ligand loss exists. See: Krafft, M. E.; Scott, I. L.; Romero, R. H.; Feibelmann, S.; Van Pelt, C. E. J. Am. Chem. Soc. 1993, 115, 7199.
28. 3-allylcobalt hydrides were postulated by Serratosa et al. as a potential mechanism for isomerization of bicyclo[3.3.0]-oct-2-enes to bicyclo[3.3.0]oct-1-enes during intermolecular Pauson-Khand reactions. See: Montaña, A.-M.; Moyano, A.; Pericàs, M. A.; Serratosa, F. Tetrahedron Lett. 1985, 41, 5995.
29. A related, albeit mechanistically different, reaction has been reported wherein 7-trimethylsilyl-6-hepten-1-ynes undergo 5-endo-dig cyclizations under the influence of halfnium (IV) chloride. Imamura, K.; Yoshikawa, E.; Gevorgyan, V.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 5339.
30. 2 = H) proved to be too unstable to the reaction conditions and gave only decomposition products.