| Summary: | Carbon–carbon bond formation by [3,3]-sigmatropic rearrangement is a fundamental and powerful method that has been used to build organic molecules for a long time. Initially, Claisen and Cope rearrangements proceeded at high temperatures with limited scopes. By introducing catalytic systems, highly functionalized substrates have become accessible for forming complex structures under mild conditions, and asymmetric synthesis can be achieved by using chiral catalytic systems. This review describes recent breakthroughs in catalytic [3,3]-sigmatropic rearrangements since 2016. Detailed reaction mechanisms are discussed to enable an understanding of the reactivity and selectivity of the reactions. Finally, this review is inspires the development of new cascade reaction pathways employing catalytic [3,3]-sigmatropic rearrangement as related methodologies for the synthesis of complex functional molecules.
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