Palladium-Catalyzed Diastereo- and Enantioselective Formal [3 + 2]-Cycloadditions of Substituted Vinylcyclopropanes

We describe a palladium-catalyzed diastereo- and enantioselective formal [3 + 2]-cycloaddition between substituted vinylcyclopropanes and electron-deficient olefins in the form of azlactone- and Meldrum’s acid alkylidenes to give highly substituted cyclopentane products. By modulation of the electro...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2012-10, Vol.134 (42), p.17823-17831
Main Authors: Trost, Barry M, Morris, Patrick J, Sprague, Simon J
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Catalysis
Crystallography, X-Ray
Cyclization
Cyclopentanes - chemical synthesis
Cyclopentanes - chemistry
Cyclopropanes - chemistry
Models, Molecular
Molecular Structure
Palladium - chemistry
Stereoisomerism
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Summary:We describe a palladium-catalyzed diastereo- and enantioselective formal [3 + 2]-cycloaddition between substituted vinylcyclopropanes and electron-deficient olefins in the form of azlactone- and Meldrum’s acid alkylidenes to give highly substituted cyclopentane products. By modulation of the electronic properties of the vinylcyclopropane and the electron-deficient olefin, high levels of stereoselectivity were obtained. The remote stereoinduction afforded by the catalyst, distal from the chiral pocket generated by the ligand, is proposed to be the result of a new mechanism invoking the Curtin–Hammett principle.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja309003x