Chiral discrimination of small substituents in biaryl atropisomer construction:enantioselective synthesis of axially chiral 1-azafluorene via Ni-catalyzed[2+2+2]cycloaddition  

作　　者：Jin-Huang Peng Yu-Qing Zheng Li-Gang Bai Wen-Bo Liu 

机构地区：[1]Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials,Engineering Research Center of Organosilicon Compounds&Materials(Ministry of Education),College of Chemistry and Molecular Sciences,Wuhan University,Wuhan 430072,China [2]Wuhan University Shenzhen Research Institute,Shenzhen 518000,China

出　　处：《Science China Chemistry》2023年第11期3148-3153,共6页中国科学（化学英文版）

基　　金：supported by the National Key Research and Development Program of China(2022YFA1502902);the National Natural Science Foundation of China(22371215,22222111,21971198);the Guangdong Basic and Applied Basic Research Foundation(2022A1515012614);the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University;China Postdoctoral Science Foundation(2022M722451)for the financial support。

摘　　要：Construction of axially chiral 1-azafluorenes via nickel-catalyzed[2+2+2]cycloaddition of alkynes and(o-alkynyl)benzyl nitriles is described.This strategy enables enantioselective discrimination of two sterically similar ortho substituents,such as H and F,during the construction of tri-ortho-substituted biaryl atropisomers.Mechanistic studies including the stereochemistry model and the stability of the atropenantiomers toward racemization are provided.The unique steric hindrance provided by 1-azafluorene skeleton and the fine chiral cavity of the nickel catalyst are key to achieving high enantioselectivity.

关 键 词：asymmetric catalysis [2+2+2]cycloaddition nickel catalysis ATROPISOMER HETEROCYCLE 

分 类 号：O621.251[理学—有机化学]