Preparation of Optically Active 2,2'-Dibromo-6,6'-diiodo-1,1'-biphenyl:A Powerful Precursor for Modular Synthesis of Functionalized Atropisomers  

作　　者：Yuanyuan Li Longhui Duan Biqiong Hong Zhenhua Gu 

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry,University of Science and Technology of China,96 Jinzhai Road,Hefei,Anhui,230026 China [2]College of Materials and Chemical Engineering,Minjiang University,Fuzhou,Fujian,350108 China

出　　处：《Chinese Journal of Chemistry》2023年第24期3515-3520,共6页中国化学（英文版）

基　　金：financial supports from National Natural Science Foundation of China(92056102);the Natural Science Foundation of Fujian Province(2023J011395).

摘　　要：The widespread applications of atropisomeric compounds have led to an increasing demand for their synthesis.Rather than synthesizing different functionalized atropisomers individually,an attractive alternative is to identify a key intermediate or precursor that can be readily elaborated and functionalized to realize divergent synthesis of this class of compounds.Building on our previous research on asymmetric ring-opening of cyclic diaryliodoniums,in this work we developed a copper-catalyzed enantioselective ring-opening reaction of ortho,ortho’-dibromo substituted cyclic diaryliodonium with lithium iodide.The resulting optically active product 2,2'-dibromo-6,6'-diiodo-1,1'-biphenyl,possessing two C—Br bonds and two C—I bonds,can be selectively advanced to form different functionalities.Remarkably,the utilities of the product were highlighted by successively demonstrating C—I and C—Br metalation,followed by carboxylation,boroylation,oxygenation,allylation,phosphinylation,etc.,all of which provide a new and convenient approach to synthesizing a range of functionalized axially chiral biphenyls.

关 键 词：ATROPISOMERISM Asymmetric catalysis Ring-opening reaction CHIRALITY Copper 

分 类 号：O62[理学—有机化学]