237. Rhodium-Catalyzed Enantioselective Vinylogous Addition of Enol Ethers to Vinyldiazoacetates

Authors: Austin G. Smith and Huw M. L. Davies

J. Am. Chem. Soc.,

2012, 134 (44), 18241–18244


A highly asymmetric vinylogous addition of acyclic silyl enol ethers to siloxyvinyldiazoacetate is described. The reaction features a diastereoselective 1,4-siloxy group migration event. Products are obtained in up to 97% ee. When more sterically crowded silyl enol ethers are employed, an enantioselective formal [3+2] cycloaddition becomes the dominant reaction pathway. Control experiments reveal the (Z)-olefin geometry to be critical for high levels of enantiocontrol.

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