Abstract
Abstract Gold catalysis is particularly efficient in mediating various kinds of sigmatropic rearrangements that either correspond to an overall transformation of a substrate or simply occur as an elementary step in a reaction sequence. Among the sigmatropic rearrangements that can be gold‐promoted, particular attention has been brought to the Cope and Claisen rearrangements, and to the rearrangement of propargylic esters, which have been the subject of numerous experimental and theoretical investigations. Compared to the thermally induced version of such rearrangements, the use of electrophilic gold species as catalysts allows significant reduction in the energy demand so that transformations can generally be performed at moderate temperature with a good control of the chemo‐ and/or stereoselectivities. This chapter gives an overview of the various synthetic methods based on the use of gold‐promoted sigmatropic rearrangements that have been reported so far.
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