Asymmetric sigmatropic rearrangement is a powerful organic transformation via substrate-reorganization to efficiently increase molecular complexity from readily accessible starting materials. In particular, a high level of diastereo- and enantioselectivity can be readily accessed through well-defined and predictable transition states in [3,3], [2,3]-sigmatropic rearrangements, which have been widely applied in the synthesis of various chiral building blocks, natural products, and pharmaceuticals. In recent years, catalytic asymmetric sigmatropic rearrangements involving chiral metal complexes to induce stereocontrol have been intensively studied. This review presents an overview of metal-catalysed enantioselective versions of sigmatropic rearrangements in the past two decades, mainly focusing on [3,3], [2,3], and [1,3]-rearrangements, to show the development of substrate design, new catalyst exploitation, and novel cascade processes. In addition, their application in the asymmetric synthesis of complex natural products is also exemplified.
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