A highly efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed,which exhibits good functional group compatibility,high atomic and step economy.This pr...A highly efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed,which exhibits good functional group compatibility,high atomic and step economy.This protocol utilizes a strategy of synergistic catalysis with a chiral N,N'-dioxide/Ni~Ⅱ complex and an achiral Pd~0 catalyst,generating a series of multisubstituted allylic alcohols with a quaternary carbon stereocenter in high yield and excellent regio-,Z/E-and enantioselectivity under mild conditions.Further transformations of the product demonstrate the potential utility of this protocol in the synthesis of allyl alcohol derivatives and natural product analogues.Experimental studies revealed that the N,N′-dioxide/metal complexes play an important role in controlling the Z/E-and enantioselectivity.The density functional theory(DFT) calculations further demonstrated that multiple C–H···π interactions between the aromatic rings of the two substrates and the amide moiety in the ligand stabilized the dominant transition state.展开更多
We report the first asymmetric three-component nucleophilic addition/dearomative[4+2]cycloaddition/isomerization cascade of transient dipoles generated from N-heteroarenes and allenoates with methyleneindolinones in t...We report the first asymmetric three-component nucleophilic addition/dearomative[4+2]cycloaddition/isomerization cascade of transient dipoles generated from N-heteroarenes and allenoates with methyleneindolinones in the presence of chiral N,N′-dioxide/metal complexes.This tandem reaction enabled rapid access to versatile chiral polycyclic N-heterocycles with good to excellent enantioselectivities under mild reaction conditions in spite of the strong background reaction,including 1,2-dihydroisoquinoline,1,2-dihydropyridine derivatives,and others.Meanwhile,a series of control experiments were conducted to elucidate the reaction mechanism and the roles of additives.展开更多
基金Supported by the basic research center grant of Shanghai Jiao Tong University(No.16JXRZ12)National Natural Science Foundation of China grant(No.81301153)+1 种基金Shanghai Mental Health Center Key Special Department grant(No.2013-YJTSZK-02)Hospital Level Project of Shanghai Mental Health Center 2014(Fund number:2014-YJ-02)
基金supported by the National Natural Science Foundation of China (U19A2014)Sichuan University(2020SCUNL204)。
文摘A highly efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed,which exhibits good functional group compatibility,high atomic and step economy.This protocol utilizes a strategy of synergistic catalysis with a chiral N,N'-dioxide/Ni~Ⅱ complex and an achiral Pd~0 catalyst,generating a series of multisubstituted allylic alcohols with a quaternary carbon stereocenter in high yield and excellent regio-,Z/E-and enantioselectivity under mild conditions.Further transformations of the product demonstrate the potential utility of this protocol in the synthesis of allyl alcohol derivatives and natural product analogues.Experimental studies revealed that the N,N′-dioxide/metal complexes play an important role in controlling the Z/E-and enantioselectivity.The density functional theory(DFT) calculations further demonstrated that multiple C–H···π interactions between the aromatic rings of the two substrates and the amide moiety in the ligand stabilized the dominant transition state.
基金the National Natural Science Foundation of China(grant no.21772127).
文摘We report the first asymmetric three-component nucleophilic addition/dearomative[4+2]cycloaddition/isomerization cascade of transient dipoles generated from N-heteroarenes and allenoates with methyleneindolinones in the presence of chiral N,N′-dioxide/metal complexes.This tandem reaction enabled rapid access to versatile chiral polycyclic N-heterocycles with good to excellent enantioselectivities under mild reaction conditions in spite of the strong background reaction,including 1,2-dihydroisoquinoline,1,2-dihydropyridine derivatives,and others.Meanwhile,a series of control experiments were conducted to elucidate the reaction mechanism and the roles of additives.
