American Chemical Society
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Mechanistic Studies on Au(I)-Catalyzed [3,3]-Sigmatropic Rearrangements using Cyclopropane Probes

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journal contribution
posted on 2009-04-01, 00:00 authored by Pablo Mauleón, Jamin L. Krinsky, F. Dean Toste
A comparative study of the Au(I)-catalyzed [3,3]-sigmatropic rearrangement of propargylic esters and propargyl vinyl ethers is described. Stereochemically defined cyclopropanes are employed as mechanistic probes to provide new synthetic and theoretical data concerning the reversibility of this type of rearrangement. Factors controlling the structure−reactivity relationship of Au(I)-coordinated allenes have been examined, thereby allowing for controlled access to orthogonal reactivity.