There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformatio...There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformations.Since all the redox reactivity of cobalt catalysis highly relies on the capability of the interconversion between their oxidation states(most frequently+1,+2 and+3),electrochemistry perfectly meets such a require ment owing to its outstanding perfo rmance in the redox manipulation.In this review,we highlight the recent advances in the merger of cobalt catalysis and electrochemistry in organic synthesis.展开更多
Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science.The direct incorporation of these elements into organic scaffolds with precise control of the oxidation state...Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science.The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H;O in the reaction mixture.展开更多
Alternating current electrolysis(ACE)is an emerging powerful synthetic tool,which principally resembles photoredox catalysis strategies.Its periodically alternating polarity feature allows oxidation and reduction proc...Alternating current electrolysis(ACE)is an emerging powerful synthetic tool,which principally resembles photoredox catalysis strategies.Its periodically alternating polarity feature allows oxidation and reduction processes to take place on the same electrode surface in a well-controlled manner via the fine-tuning of current frequency along with other reaction parameters.Therefore,many challenging transformations in typical direct electrolysis,including constant current electrolysis or constant potential electrolysis,could be achieved via ACE.The recent advances in the organic synthesis using this emerging technology and its advantages over direct electrolysis are highlighted.展开更多
基金Financial support from the National Natural Science Foundation of China(No.21901041)Fuzhou University(No.510841)is gratefully acknowledged。
文摘There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformations.Since all the redox reactivity of cobalt catalysis highly relies on the capability of the interconversion between their oxidation states(most frequently+1,+2 and+3),electrochemistry perfectly meets such a require ment owing to its outstanding perfo rmance in the redox manipulation.In this review,we highlight the recent advances in the merger of cobalt catalysis and electrochemistry in organic synthesis.
基金Financial support from the National Natural Science Foundation of China (Nos. 21901041 and 21772023)State Key Laboratory of Physical Chemistry of Solid Surfaces,Xiamen University (No.202008)Fuzhou University (No. 510841)。
文摘Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science.The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H;O in the reaction mixture.
基金This work was supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.NRF-2021R1C1C1004605)(H.Kim)the National Natural Science Foundation of China(Nos.22171046,21901041)(K.Y).
文摘Alternating current electrolysis(ACE)is an emerging powerful synthetic tool,which principally resembles photoredox catalysis strategies.Its periodically alternating polarity feature allows oxidation and reduction processes to take place on the same electrode surface in a well-controlled manner via the fine-tuning of current frequency along with other reaction parameters.Therefore,many challenging transformations in typical direct electrolysis,including constant current electrolysis or constant potential electrolysis,could be achieved via ACE.The recent advances in the organic synthesis using this emerging technology and its advantages over direct electrolysis are highlighted.
