Catalytic diastereoselective construction of multiple contiguous quaternary carbon stereocenters via [2+2] cycloaddition and mechanistic insight

作     者：Xi Wang Fujie Liu Tao Xu Xi Wang;Fujie Liu;Tao Xu

作者机构：Molecular Synthesis Center&Key Laboratory of Marine DrugsMinistry of EducationSchool of Medicine and PharmacyOcean University of ChinaQingdao 266003China Laboratory for Marine Drugs and BioproductsPilot National Laboratory for Marine Science and TechnologyQingdao 266237China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2023年第34卷第3期

页      面：288-292页

核心收录：

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.82122063,81991522 and 81973232) Shandong Science Fund for Distinguished Young Scholars(No.ZR2020JQ32) the Fundamental Research Funds for the Central Universities(No.202041003)。 

主　　题：Contiguous quaternary carbon stereocenters [2+2]Cycloaddition Fused ring system 

摘      要：Multiple contiguous quaternary carbon stereocenters(CQS) are highly challenging, yet important structural motifs in organic synthesis. Here, we describe a visible light induced catalytic [2 + 2] cycloaddition approach that constructed up to four CQS in a pentacyclic fused ring system diastereoselectively, from the readily accessible dienamides with pendent heteroaryls. Variously substituted dienamides have been cyclized with heteroaryls to provide a range of novel CQS-containing scaffolds(26 examples, up to 96%yield and 20:1 dr ratio). Mechanistic studies revealed that it may proceed through an uncommon β-C radical initiated 7-endo cyclization from the biradical intermediate.