Here,we describe a strategy for the copper-catalyzed asymmetric heteroarylation of yne-thiophene carbonates with indoles via remote substitution.The key to the success of this strategy lies in the design of the alkyny...Here,we describe a strategy for the copper-catalyzed asymmetric heteroarylation of yne-thiophene carbonates with indoles via remote substitution.The key to the success of this strategy lies in the design of the alkynyl group at the ortho-position of the heterocycle thiophene,enabling the formation of a triarylmethane moiety via very remote substitution.Thus,the concept of remote copper-catalyzed asymmetric transformation extends not only to yne-allylic esters but also to yne-aryl esters.The reaction readily provides a diverse array of chiral triarylmethanes with high efficiency,enantioselectivity,and excellent functional group compatibility.Moreover,facile follow-up transformations underscore their potential utility in the synthesis of various enantioenriched building blocks.Preliminary mechanistic studies support the plausibility of the remote substitution pathway.展开更多
Rhodium(III)catalysis has set the stage for a plethora of oxidative C–H functionalizations over the last decade,which have predominantly employed stoichiometric amounts of toxic and expensive metal oxidants,such as s...Rhodium(III)catalysis has set the stage for a plethora of oxidative C–H functionalizations over the last decade,which have predominantly employed stoichiometric amounts of toxic and expensive metal oxidants,such as silver(I)salts.In the meantime,electrosynthesis has emerged as an increasingly viable alternative for expensive and toxic oxidants.Recently,significant momentum has been achieved with the merger of electrocatalysis with organometallic C–H activation.However,user-friendly and robust rhodaelectro-catalysis has until very recently proven elusive for oxidative C–H activations.This minireview highlights the current knowledge and recent advances of electrooxidation in rhodium-catalyzed C–H or C–C activations,with a topical focus on contributions from the Ackermann group through July 2020.展开更多
Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Her...Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.展开更多
基金supported by the National Natural Science Foundation of China(21801087,22201089)。
文摘Here,we describe a strategy for the copper-catalyzed asymmetric heteroarylation of yne-thiophene carbonates with indoles via remote substitution.The key to the success of this strategy lies in the design of the alkynyl group at the ortho-position of the heterocycle thiophene,enabling the formation of a triarylmethane moiety via very remote substitution.Thus,the concept of remote copper-catalyzed asymmetric transformation extends not only to yne-allylic esters but also to yne-aryl esters.The reaction readily provides a diverse array of chiral triarylmethanes with high efficiency,enantioselectivity,and excellent functional group compatibility.Moreover,facile follow-up transformations underscore their potential utility in the synthesis of various enantioenriched building blocks.Preliminary mechanistic studies support the plausibility of the remote substitution pathway.
基金support by the Deutsche Forschungsgemeinschaft(German Research Foundation)(Gottfried-Wilhelm-Leibniz award to L.A.)and the China Scholarship Council(fellowship to C.Z.)is gratefully acknowledged.
文摘Rhodium(III)catalysis has set the stage for a plethora of oxidative C–H functionalizations over the last decade,which have predominantly employed stoichiometric amounts of toxic and expensive metal oxidants,such as silver(I)salts.In the meantime,electrosynthesis has emerged as an increasingly viable alternative for expensive and toxic oxidants.Recently,significant momentum has been achieved with the merger of electrocatalysis with organometallic C–H activation.However,user-friendly and robust rhodaelectro-catalysis has until very recently proven elusive for oxidative C–H activations.This minireview highlights the current knowledge and recent advances of electrooxidation in rhodium-catalyzed C–H or C–C activations,with a topical focus on contributions from the Ackermann group through July 2020.
基金financial support from the National Natural Science Foundation of China (No.21801087)Fundamental Research Funds for the Central Universities CCNU (No.CCNU19QN064)+2 种基金the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)the Key Scientific and Technological Project of Henan Province (No.212102311068)。
文摘Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.
