Hao Yu, Li Zi-Hao, Ma Zhi-Gang, Liu Ru-Xin, Ge Rui-Tian, Li Quan-Zhe, Ding Tong-Mei, Zhang Shu-Yu
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University Shanghai 200240 P. R. China
Chem Sci. 2023 Aug 16;14(35):9496-9502. doi: 10.1039/d3sc02705h. eCollection 2023 Sep 13.
An axially chiral styrene-based organocatalyst, featuring a combination of axially chiral styrene-based structure and a pyrrole ring, has been designed and synthesized. This catalyst demonstrates remarkable capabilities in producing a wide range of densely substituted spirooxindoles that feature an alkyne-substituted quaternary stereogenic center. These spirooxindoles are generated through mild cascade Michael/cyclization reactions, resulting in high conversion rates and exceptional enantioselectivity. Our catalytic model, based on experiments, X-ray structure analysis and DFT calculations suggests that chiral matched π-π interactions and multiple H-bonds between the organocatalyst and substrates play significant roles in controlling the stereoselectivity of the reaction.
一种具有轴手性苯乙烯基结构和吡咯环组合的轴手性苯乙烯基有机催化剂已被设计并合成。该催化剂在制备一系列具有炔烃取代季立体中心的高度取代螺环氧化吲哚方面表现出卓越的能力。这些螺环氧化吲哚是通过温和的串联迈克尔/环化反应生成的，具有高转化率和出色的对映选择性。基于实验、X射线结构分析和密度泛函理论计算的催化模型表明，有机催化剂与底物之间的手性匹配π-π相互作用和多个氢键在控制反应的立体选择性方面发挥着重要作用。
