Silver-catalyzed unstrained C(CO)–alkyl bond scission via[3+2]/retro-[3+2]cycloaddition of ketones with N-isocyanoiminotriphenylphosphorane

作     者：Zikun Wang Linxuan Li Xueying Zhang Xihe Bi Zikun Wang;Linxuan Li;Xueying Zhang;Xihe Bi

作者机构：Department of ChemistryNortheast Normal UniversityChangchun 130024China State Key Laboratory of Elemento-Organic ChemistryNankai UniversityTianjin 300071China 

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

年 卷 期：2021年第64卷第7期

页      面：1157-1163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：provided by the National Natural Science Foundation of China(21871043,21961130376) Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH,20200801065GH) the Fundamental Research Funds for the Central Universities(2412019ZD001,2412019FZ006)。 

主　　题：silver-catalyzed C-C bond scission unstrained ketones tertiary alcohol intermediates cycloaddition 

摘      要：C(CO)–alkyl bonds are ubiquitous in a variety of organic molecules,and their selective activation and functionalization are important for the reconstruction of simple ketones into valuable building blocks.However,due to the thermodynamic and kinetic stability,the cleavage and transformation of the unstrained C(CO)–alkyl bonds remain a significant challenge.Herein,we report a novel silver-catalyzed scission of the unstrained C(CO)–alkyl bond of ketones by reacting with N-isocyanoiminotriphenylphosphorane(NIITP)under mild conditions.This method could transform a variety of unstrained ketones into iminophosphoranes and nitriles in high yields.Experimental and computational studies disclosed the reaction proceeded through an unprecedented[3+2]/retro-[3+2]cycloaddition mechanism.