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
• 来源期刊: 中国科学：化学（英文版）
• 年，卷（期）: 2021,（7）
• 所属期刊栏目: COMMUNICATIONS
• 页码范围: 1157-1163
• 页数: 7页
• 语种: 英文

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-isocyanoiminotriphenyl-phosphorane(NI1TP)under mild conditions.This method could transform a variety of unstrained ketones into iminopho-sphoranes and nitriles in high yields.Experimental and computational studies disclosed the reaction proceeded through an unprecedented[3+2]/retro-[3+2]cycloaddition mechanism.