Abstract
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.
Highlights
We summarize the developments in the catalytic Claisen and Cope rearrangements since 2016
We describe the detailed mechanism of transition metal-mediated reactions in order to provide deeper understanding of the specific reactivity of metals as well as the regio- and stereoselective pathways
2016, they achieved the kinetic resolution of racemic propargyl vinyl ethers by asymIn 2016, they achieved the kinetic resolution of racemic propargyl vinyl ethers asymmetric propargyl Claisen rearrangement in the presence of Ni(II) species and the chiral
Summary
C. Cope in 1940 [8], Cope rearrangement, including the reaction with hetero-analogues, has been extensively studied for application in synthesis, as well as from the theoretical perspective [9,10,11]. Cope in 1940 [8], Cope rearrangement, including the reaction with hetero-analogues, has been extensively studied for application in synthesis, as well as from the theoretical perspective [9,10,11] Both representative [3,3]-sigmatropic rearrangements have remained powerful tools in organic synthesis for a long time, and a variety of catalytic versions of these rearrangement reactions were recently developed to achieve the highly reactive and enantioselective synthesis of functionalized molecules by overcoming the limits of the common thermal pathway [12,13,14,15].
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