Tetrasubstituted olefins are significant scaffolds as they are prevalent in many biologically active compounds and versatile building blocks for organic synthesis. Herein, we report an electrochemical oxidative Csp^3...Tetrasubstituted olefins are significant scaffolds as they are prevalent in many biologically active compounds and versatile building blocks for organic synthesis. Herein, we report an electrochemical oxidative Csp^3—H/S—H cross-coupling reaction, in which various tetrasubstituted olefins were prepared under base-free, transition metal-free, and oxidants-free reaction conditions.展开更多
Summary of main observation and conclusion An efficient and environmentally benign electrochemical oxidative radical C-H trifluoromethylation of arenes by employing Langlois reagent as the CF3 source was developed in ...Summary of main observation and conclusion An efficient and environmentally benign electrochemical oxidative radical C-H trifluoromethylation of arenes by employing Langlois reagent as the CF3 source was developed in this work.Neither transition metal catalysts nor external chemical oxidants were required in this trifluoromethylation process.The reaction could be conducted in gram scale with high reaction efficiency.展开更多
Since tetrasubstituted olefins serve as the key structure motifs in a large number of biologically active compounds,methods for synthesis of tetrasubstituted olefins are highly desirable.Among various synthetic method...Since tetrasubstituted olefins serve as the key structure motifs in a large number of biologically active compounds,methods for synthesis of tetrasubstituted olefins are highly desirable.Among various synthetic methodologies,the most known strategies are the functionalization of olefins,alkynes,and allenes.For example,Zhang,Gosselin and co-workers prepared a series of tetrasubstituted olefins via Suzuki-Miyaura coupling (Scheme 1a).[1] Morandi and co-workers reported a palladium-catalyzed intermolecular aryliodination of internal alkynes (Scheme 1b).[2] Ma and co-workers prepared a series of tetrasubstituted olefins by using readily available organozinc reagents and 2,3-allenals (Scheme 1c).[3] Despite extensive advances,the reported methods often require pre-prepared starting materials,inevitably leading to some by-products.Recently,under the supervision of Prof.Wang and Lei,we and Yang et al.reported an unprecedented electrochemical oxidative Csp3-H/S-H cross-coupling reaction between thiophenols and acetonitrile (Scheme 1d),yielding a series of tetrasubstituted olefins under exogenous-oxidant-free conditions.展开更多
Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential i...Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential in running decarboxylation to construct ketone derivatives.In this article,we have developed a photocatalytic decarboxylative cross-coupling ofα-oxocarboxylic acids and olefins to the synthesis of diverse aryl ketones.Various alkenes andα-oxocarboxylicacids were compatible,generating the desired products in up to 90%yield.Preliminary mechanism studies suggest that a free radical pathway is involved in this process.展开更多
基金the National Natural Science Foundation of China (Nos.21562026,21762025,21702027)the Natural Science Foundation of Jiangxi Province (No.20161BAB203085) for financial support.
文摘Tetrasubstituted olefins are significant scaffolds as they are prevalent in many biologically active compounds and versatile building blocks for organic synthesis. Herein, we report an electrochemical oxidative Csp^3—H/S—H cross-coupling reaction, in which various tetrasubstituted olefins were prepared under base-free, transition metal-free, and oxidants-free reaction conditions.
基金supported by the National Natural Science Foundation of China (No.21702081)Jiangxi Provincial Education Department Foundation (No.GJJ160325).
文摘Summary of main observation and conclusion An efficient and environmentally benign electrochemical oxidative radical C-H trifluoromethylation of arenes by employing Langlois reagent as the CF3 source was developed in this work.Neither transition metal catalysts nor external chemical oxidants were required in this trifluoromethylation process.The reaction could be conducted in gram scale with high reaction efficiency.
文摘Since tetrasubstituted olefins serve as the key structure motifs in a large number of biologically active compounds,methods for synthesis of tetrasubstituted olefins are highly desirable.Among various synthetic methodologies,the most known strategies are the functionalization of olefins,alkynes,and allenes.For example,Zhang,Gosselin and co-workers prepared a series of tetrasubstituted olefins via Suzuki-Miyaura coupling (Scheme 1a).[1] Morandi and co-workers reported a palladium-catalyzed intermolecular aryliodination of internal alkynes (Scheme 1b).[2] Ma and co-workers prepared a series of tetrasubstituted olefins by using readily available organozinc reagents and 2,3-allenals (Scheme 1c).[3] Despite extensive advances,the reported methods often require pre-prepared starting materials,inevitably leading to some by-products.Recently,under the supervision of Prof.Wang and Lei,we and Yang et al.reported an unprecedented electrochemical oxidative Csp3-H/S-H cross-coupling reaction between thiophenols and acetonitrile (Scheme 1d),yielding a series of tetrasubstituted olefins under exogenous-oxidant-free conditions.
基金supported by the National Natural Science Foundation of China(21520102003,21702081,21702152)the Hubei Province Natural Science Foundation of China(2017CFA010)the Program of Introducing Talents of Discipline to Universities of China(111 Program)
文摘Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential in running decarboxylation to construct ketone derivatives.In this article,we have developed a photocatalytic decarboxylative cross-coupling ofα-oxocarboxylic acids and olefins to the synthesis of diverse aryl ketones.Various alkenes andα-oxocarboxylicacids were compatible,generating the desired products in up to 90%yield.Preliminary mechanism studies suggest that a free radical pathway is involved in this process.
