Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed ...Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed as one of the most efficient methods for selective C–H functionalization. Although a great progress has been made by utilizing this traditional method, developing new strategy for selective C–H bond functionalization is still highly demanded. Hence, a novel oxidation-induced C–H bond functionalization method was demonstrated in this work. By this new method, ortho-C(sp2)–H chlorination of N-substituted 2-naphthylamine was realized in a highly selective manner.展开更多
In the past decade,transition-metal-catalyzed C–H functionalization by weak coordination has emerged as a practical and powerful tool to access many valuable chemicals.Two classes of weakly coordinating directing gro...In the past decade,transition-metal-catalyzed C–H functionalization by weak coordination has emerged as a practical and powerful tool to access many valuable chemicals.Two classes of weakly coordinating directing groups,commonly occurring functional groups,and easily removable auxiliaries,have been found to be efficient and practical for C–H activation reactions.This mini-review contains examples of recent research advances on transition-metal-catalyzed SP2 C–H functionalization via weak coordination,using Ru,Rh,and Pd.A number of weakly coordinating functional groups(e.g.,ketone,ester,carbamate,tertiary amide,ether,thioether,alcohol,and some others)are covered.As the field of transition-metal-catalyzed C–H functionalization continues to develop and more synthetically useful chemo-,regio-,and enantioselective reactions catalyzed by transition metal via weak coordination are discovered,this promising and attractive strategy will play a more important role in modern organic synthesis.展开更多
A highly efficient and chemoselective dual functionalization of unprotected phenols withα-orβ-hydroxyl acids is presented.A variety of valuable benzofuranones and dihydrocoumarins are delivered in moderate to high y...A highly efficient and chemoselective dual functionalization of unprotected phenols withα-orβ-hydroxyl acids is presented.A variety of valuable benzofuranones and dihydrocoumarins are delivered in moderate to high yields.Density functional theory(DFT)calculations and control experiments indicate that an untypical Friedel–Crafts alkylation and the subsequent lactonization are catalyzed by the Lewis acid form and the Brønsted acid form of borane,respectively.Gram-scale experiments and late-stage functionalization of complex molecules have been performed to highlight the utility of this reaction.展开更多
基金supported by the National Natural Science Foundation of China (21390402, 21520102003, 21702150)the National Basic Research Program of China (2012CB725302)+1 种基金the CAS Interdisciplinary Innovation Team and the Hubei Province Natural Science Foundation of China (2017CFA010)China Postdoctoral Science Foundation (BX201600114, 2016M602340)
文摘Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed as one of the most efficient methods for selective C–H functionalization. Although a great progress has been made by utilizing this traditional method, developing new strategy for selective C–H bond functionalization is still highly demanded. Hence, a novel oxidation-induced C–H bond functionalization method was demonstrated in this work. By this new method, ortho-C(sp2)–H chlorination of N-substituted 2-naphthylamine was realized in a highly selective manner.
基金supported by the National Basic Research Program of China(2011CB965300)the National Natural Science Foundation of China(21142008,21302106)Tsinghua University 985 Phase II Funds,and the Tsinghua University Initiative Scientific Research Program
文摘In the past decade,transition-metal-catalyzed C–H functionalization by weak coordination has emerged as a practical and powerful tool to access many valuable chemicals.Two classes of weakly coordinating directing groups,commonly occurring functional groups,and easily removable auxiliaries,have been found to be efficient and practical for C–H activation reactions.This mini-review contains examples of recent research advances on transition-metal-catalyzed SP2 C–H functionalization via weak coordination,using Ru,Rh,and Pd.A number of weakly coordinating functional groups(e.g.,ketone,ester,carbamate,tertiary amide,ether,thioether,alcohol,and some others)are covered.As the field of transition-metal-catalyzed C–H functionalization continues to develop and more synthetically useful chemo-,regio-,and enantioselective reactions catalyzed by transition metal via weak coordination are discovered,this promising and attractive strategy will play a more important role in modern organic synthesis.
基金to the National Natural Science Foundation of China(no.21903089)the Research Foundation for Natural Science of Guangdong Province(no.2018A0303130178)+1 种基金the Advanced Talents of Sun Yat-sen University(no.36000-18821101)the Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery(no.2019B030301005)for financial support of this program.
文摘A highly efficient and chemoselective dual functionalization of unprotected phenols withα-orβ-hydroxyl acids is presented.A variety of valuable benzofuranones and dihydrocoumarins are delivered in moderate to high yields.Density functional theory(DFT)calculations and control experiments indicate that an untypical Friedel–Crafts alkylation and the subsequent lactonization are catalyzed by the Lewis acid form and the Brønsted acid form of borane,respectively.Gram-scale experiments and late-stage functionalization of complex molecules have been performed to highlight the utility of this reaction.
