Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates

Journal of the American Chemical Society

Volumn 127, Issue 36, 2005, Pages 12466-12467

  Evans, P Andrew ^a   Lai, Kwong Wan ^a   Sawyer, James R ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

RHODIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CYCLIZATION; ENANTIOSELECTIVITY; MOLECULAR INTERACTION; REACTION ANALYSIS;

ALKYNES; CATALYSIS; CYCLIZATION; HETEROCYCLIC COMPOUNDS, 2-RING; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PROPIONATES; RHODIUM; STEREOISOMERISM;

EID: 24744435554     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja053123y     Document Type: Article

References (22)

1. For recent reviews on metal-catalyzed carbocyclization reactions, see: (a) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813.
2. (b) Nakamura, I.; Yamamoto, Y. Chem. Rev. 2004, 104, 2127.
3. For recent reviews on metal-mediated [2+2+2] carbocyclizations, see: (a) Malacria, M.; Aubert, C.; Renaud J. L. In Science of Synthesis: Houben-Weyl Methods for Molecular Transformations; Lautens, M., Trost, B. M., Eds.; Georg Thieme Verlag: New York, 2001; Vol. 1. pp 439-530.
4. (b) Varela, J.; Saá, C. Chem. Rev. 2003, 103, 3787.
5. (c) Fujiwara, M.; Ojima, I. In Modern Rhodium-Catalyzed Organic Reactions;, Evans, P. A., Ed.; 2005; Chapter 7, pp 129-150 and pertinent references therein.
6. For pioneering work on the rhodium-catalyzed intermolecular [2+2+2] carbocylization using tethered 1,6-diynes and 1,6-enynes, see: (a) Grigg, R.; Scott, R.; Stevenson, P. J. Chem. Soc., Perkin Trans, 1 1988, 1357.
7. (b) Grigg, R.; Scott, R.; Stevenson, P. J. Chem. Soc., Perkin Trans. 1 1988, 1365.
8. For a recent example of a rhodium-catalyzed [2+2+2] dimerization of 1,6-enynes, see: Oh, C. H.; Sung, H. R.; Jung, S. H.; Lim, Y. M. Tetrahedron Lett. 2001, 42, 5493.
9. For examples of an intermolecular metal-catalyzed [2+2+2] carbocyclization with various 1,6-enynes using symmetrical alkynes, see: (a) Pd: Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1987, 109, 4753.
10. (b) Ir: Kezuka, S.; Okado, T.; Niou, E.; Takeuchi, R. Org. Lett. 2005, 7, 1711.
11. (c) Rh: Evans, P. A.; Sawyer, J. R.; Lai, K. W.; Huffman, J. C. Chem. Commun. 2005, 3971.
12. For an example of an intermolecular cobalt-mediated [2+2+2] carbocyclization with various 1,6-enynes using an unsymmetrical alkyne, see: Chang, C.-A.; King, J. A., Jr.; Vollhardt, K. P. C. J. Chem. Soc., Chem. Commun. 1981, 53.
13. 4 precatalyst in terms of chemical yield.
14. For an excellent review on the development of chiral bisphosphine ligands. see: Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron 2005, 61, 5405 and pertinent references therein.
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18. 4 (9.7 mg, 20 mol %) were suspended in anhydrous THF (1.0 mL) and stirred at room temperature under an atmosphere of argon for ca. 10 min. (S)-Xyl-P-PHOS (22.7 mg, 12 mol %) in anhydrous THF (3.0 mL) was then added to the yellow suspension, and the mixture was stirred at room temperature for an additional ca. 30 min. Methyl phenylpropiolate (120.1 mg, 0.75 mmol) was added in one portion, followed by addition of 1,6-enyne 1a (62.3 mg, 0.25 mmol) in anhydrous THF (2.0 mL) via syringe pump over ca. 2 h at 60 °C, followed by an additional ca. 30 min (TLC control). The reaction mixture was allowed to cool to room temperature, and the resultant mixture was filtered through a short pad of silica gel (eluting with 50% ethyl acetate/hexanes) and concentrated in vacua to afford the crude product. Purification by flash chromatography (silica gel, eluting with a 10-30% ethyl acetate/hexanes gradient) afforded the bicyclohexadienes 2a/3a (94.1 mg, 98%) as a white solid, with 10:1 regioselectivity and 97% ee.
19. The absolute configuration was made by analogy with (S)-2a, which was determined by X-ray crystallography.
20. For recent reviews on the enantioselective construction of quaternary carbon stereocenters, see: (a) Christoffers, J.; Mann, A. Angew. Chem., Int. Ed. 2001, 40, 4591.
21. (b) Denissova, I.; Barriault, L. Tetrahedron 2003, 59, 10105 and pertinent references therein.
22. 2)Me (rs = 10:1, 97% ee, 66%).