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Volumn 13, Issue 22, 2007, Pages 6437-6451

[(NHC)AuI]-catalyzed formation of conjugated enones and enals: An experimental and computational study

Author keywords

Carbenes; Density functional calculations; Enones; Gold; Potential energy surface

Indexed keywords

DENSITY FUNCTIONAL THEORY; GOLD; OPTIMIZATION; SOLVENTS; STEREOSELECTIVITY;

EID: 34547556193     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200700134     Document Type: Article
Times cited : (162)

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    • In addition, the formation of 3 a from 6 seems to exclude a mechanism in which the oxonium intermediate of the 1,3-shift would be trapped by water, forming an ortho-ester-like intermediate that would rearrange to the enone see scheme below, unless two distinct mechanisms are in action for propargylic ethers and esters. This hypothesis is currently being investigated. equation presented at
    • In addition, the formation of 3 a from 6 seems to exclude a mechanism in which the oxonium intermediate of the 1,3-shift would be trapped by water, forming an ortho-ester-like intermediate that would rearrange to the enone (see scheme below), unless two distinct mechanisms are in action for propargylic ethers and esters. This hypothesis is currently being investigated. equation presented at
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    • We would like to thank a referee for drawing our attention to the crucial issue of the formation of HSbF6, its form in solution and the role it might play under the reaction conditions
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    • Commercially available from Aldrich
    • Commercially available from Aldrich.
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    • The assignment of the (Z)-olefin relies on the signals of the two vinylic protons (δ = 6.81 (dt, J=11.6, 1.7Hz, 1H; CH=CH-C=O), 6.33 ppm (dt, J = 11.6, 7.4 Hz, 1H; CH=CH-C=O)). For full characterization of this compound, see: S. Watanabe, T. Arai, H. Sasai, M. Bougauchi, M. Shibasaki, J. Org. Chem. 1998, 63, 8090-8091.
    • The assignment of the (Z)-olefin relies on the signals of the two vinylic protons (δ = 6.81 (dt, J=11.6, 1.7Hz, 1H; CH=CH-C=O), 6.33 ppm (dt, J = 11.6, 7.4 Hz, 1H; CH=CH-C=O)). For full characterization of this compound, see: S. Watanabe, T. Arai, H. Sasai, M. Bougauchi, M. Shibasaki, J. Org. Chem. 1998, 63, 8090-8091.
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