Construction of Vicinal All-Carbon Stereogenic Centers via Copper-Catalyzed Asymmetric Decarboxylative Propargylation: Enantio- and Diastereoselective Synthesis of Substituted Spirolactones

作者：Sheng Zuo, Yuan Tao, Zhigang Liu, Ke Zhang, Luyun Zhang, Yingtang Ning, Fen‐Er Chen · 发表于：Organic Letters · 年份：2023 · DOI：10.1021/acs.orglett.2c04113 · 被引用次数：21 · 研究领域：Asymmetric Synthesis and Catalysis、Synthetic Organic Chemistry Methods、Chemical synthesis and alkaloids

The formation of vicinal all-carbon quaternary stereocenters remains a formidable challenge. We report herein the synthesis of such highly congested structural dyads by copper-catalyzed decarboxylative propargylation between propargyl carbonates and indanone-based nucleophiles. The implementation of diphenylethylenediamine (DPEN)-based ligands is the key to success. A wide range of functional groups was tolerated, delivering the indanone-based spirolactones in good yields with high diastereo- and enantioselectivity. The mechanistic observations suggest the capability of the new copper complex to enable stereocontrolled addition to copper-allenylidene species.