Catalytic Asymmetric Diels–Alder Reaction/[3,3] Sigmatropic Rearrangement Cascade of 1‐Thiocyanatobutadienes

作者：Yuhang Zhou, Lili Lin, Xiaohua Liu, Xinyue Hu, Yan Lu, Xiying Zhang, Xiaoming Feng · 发表于：Angewandte Chemie International Edition · 年份：2018 · DOI：10.1002/anie.201804811 · 被引用次数：35 · 研究领域：Asymmetric Synthesis and Catalysis、Synthesis and Catalytic Reactions、Organic Chemistry Cycloaddition Reactions

A highly efficient asymmetric Diels-Alder/[3,3] sigmatropic rearrangement reaction of methyleneindolinones with 1-thiocyanatobutadienes has been realized by using a chiral N,N'-dioxide/nickel(II) complex as the catalyst. A range of cyclohexenyl isothiocyanates were synthesized in high yields with excellent diastereo- and enantioselectivities. Based on mechanistic studies, a catalytic cycle with possible transition-state models were proposed to explain the process.