An unprecedented synthesis of axially chiral biaryls by rearrangement and aromatization of carbocations with central-to-axial conversion of chirality

作     者：Qi Liu Xue-Dong Li Liang Cheng Li Liu 

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)CAS Key Laboratory of Molecular Recognition and FunctionCAS Research/Education Center for Excellence in Molecular SciencesInstitute of ChemistryChinese Academy of SciencesBeijing 100190China University of Chinese Academy of SciencesBeijing 100049China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第9期

页      面：2998-3003页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(22022704 21977097 22271291) Chinese Academy of Sciences 

主　　题：br?nsted acid catalysis desymmetrization phosphoric acid axially chiral biaryls central-to-axial conversion 

摘      要：The central-to-axial chirality conversion represents a fascinating class of chemical processes consisting of the destruction of stereogenic centers and the simultaneous installation of axial chiral elements,which provides efficient methods for the preparation of axially chiral ***,developing catalytic asymmetric approaches for constructing these central chirality precursors and the efficient central-to-axial chirality conversion remains a challenge due to the requirement of aromatization or elimination *** this work,we have developed an unprecedented enantioselective intramolecular FriedelCrafts alkylation with unactivated-ketone carbonyls from which a chiral tertiary alcohol was generated with high efficiency and excellent *** addition,the central-to-axial chirality conversion strategy has been successfully applied to the synthesis of enantioenriched biaryls via a less-explored carbocation-initiated rearrangement and aromatization under the promotion of Lewis *** methodology provided a straightforward and sustainable access to a broad range of biaryl-2-carboxylic acid and in excellent yields(up to 92%)and excellent central-to-axial chirality conversion(up to 99%conversion percentage).This work could be a great model for developing new methods for synthesizing axially chiral biaryls and a general protocol for the rearrangement and aromatization of carbocations for further functionalization.