Herein,a nickel-catalyzed arylcyanation of unactivated alkenes via cyano group translocation with aryl boronic acids has been developed.These transformations provided a robust approach to constructing structurally div...Herein,a nickel-catalyzed arylcyanation of unactivated alkenes via cyano group translocation with aryl boronic acids has been developed.These transformations provided a robust approach to constructing structurally diverse 1,n-dinitriles or 4-amino nitriles from easily prepared and commercially available starting materials.The cyano group translocation was achieved,involving the addition into the intramolecular C–N triple bond followed by the retro-Thorpe reaction.Mechanistic studies revealed that high temperature and CsHCO_(3) as the base were crucial for the cyano group translocation.展开更多
The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl...The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).展开更多
基金supported by the National Natural Science Foundation of China(21971074,22001076)the Natural Science Foundation of Guangdong Province(2022A1515010660,2021A1515220024)the Natural Science Foundation of Guangzhou(202102020982)。
文摘Herein,a nickel-catalyzed arylcyanation of unactivated alkenes via cyano group translocation with aryl boronic acids has been developed.These transformations provided a robust approach to constructing structurally diverse 1,n-dinitriles or 4-amino nitriles from easily prepared and commercially available starting materials.The cyano group translocation was achieved,involving the addition into the intramolecular C–N triple bond followed by the retro-Thorpe reaction.Mechanistic studies revealed that high temperature and CsHCO_(3) as the base were crucial for the cyano group translocation.
基金We are grateful for financial support from the National Nature Science Foundation of China(Nos.21532009,91956202,21821002 and 21790330)the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417000,19590750400 and 17JC1401200)+2 种基金the strategic Priority Research Program(No.XDB20000000)the Key Research Program of Frontier Science(QYZDJSSWSLH055)the International Partnership Program(No.121731KY5B20190016)of the Chinese Academy of Sciences.
文摘The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).
