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Mechanistic studies on Au(I)-catalyzed [3,3]-sigmatropic rearrangements using cyclopropane probes.

ABSTRACT: 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.

SUBMITTER: Mauleon P

PROVIDER: S-EPMC2666792 | biostudies-literature | 2009 Apr

REPOSITORIES: biostudies-literature

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Mechanistic studies on Au(I)-catalyzed [3,3]-sigmatropic rearrangements using cyclopropane probes.

Mauleón Pablo P Krinsky Jamin L JL Toste F Dean FD

Journal of the American Chemical Society 20090401 12

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. ...[more]

PMID: 19275228

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