The allenic Pauson-Khand cycloaddition. Dependence in π-bond selectivity on substrate structure

Tetrahedron Letters

Volumn 39, Issue 9, 1998, Pages 931-934

  Brummond, Kay M ^a   Wan, Honghe ^a  

^a WEST VIRGINIA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLENE DERIVATIVE; MOLYBDENUM;

ARTICLE; CATALYSIS; CHIRALITY; CYCLIZATION; ENZYME SPECIFICITY; STEREOCHEMISTRY; STRUCTURE ACTIVITY RELATION;

EID: 0032568050     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10679-7     Document Type: Article

References (17)

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3. 3. McMorris, T. C.; Keiner, M. J.; Wang, W.; Estes, L. A.; Montoya, M. A.; Taetle, R. J. Org. Chem. 1992, 57, 6876-6883;
4. McMorris, T. C.; Hu, Y.; Yu, J.; Keiner, M. Chem. Commun. 1997, 315-316.
5. 4. This research was presented at the 35th National Organic Symposium, June 23, 1997, San Antonio, Texas, Poster M131.
6. 5. Jeong, N.; Lee, S. J.; Lee, B. Y.; Chung, K. Y. Tetrahedron Lett. 1993, 34, 4027-4030.
7. 6. Sample experimental details for the allenic P-K reaction: A mixture of 6,7-pentadecadien-1-yne (57 mg, 0.28 mmol), molybdenum carbonyl (118 mg, 0.45 mmol) and DMSO (200 μL, 2.8 mmol) in toluene (3 mL) was heated at 100 °C under argon for 15 h, during which a dark blue precipitate formed. The reaction mixture was passed through a small plug of silica gel eluting with ethyl acetate/hexane (1:1). The filtrate was concentrated in vacuo and the residue chromatographed on silica gel (eluting with 5% ethyl acetate/hexane) to furnish Z-4-[(heptyl)methylidenyl]-bicyclo[3.3.0]oct-1-en-3-one (15 mg, 25%) and E-4-[(heptyl)methylidenyl]-bicyclo[3.3.0]oct-1-en-3-one (28 mg, 50%).
8. 13C NMR, GCTMS).
9. +), 203, 189, 161, 147, 134, 106, 91, 77.
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11. 8/NMO: Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281-5284. These reactions suffered from low yields and a general lack of π-bond selectivity.
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