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

作　　者：Xi Wang Fujie Liu Tao Xu 

机构地区：[1]Molecular Synthesis Center&Key Laboratory of Marine Drugs,Ministry of Education,School of Medicine and Pharmacy,Ocean University of China,Qingdao 266003,China [2]Laboratory for Marine Drugs and Bioproducts,Pilot National Laboratory for Marine Science and Technology,Qingdao 266237,China

出　　处：《Chinese Chemical Letters》2023年第3期288-292,共5页中国化学快报（英文版）

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)。

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.

关 键 词：Contiguous quaternary carbon stereocenters [2+2]Cycloaddition Fused ring system 

分 类 号：O621.251[理学—有机化学]