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
The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The...The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).展开更多
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China cShanghai Hong Kong Joint Laboratory in Chemical Synthesis, Shan...bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China cShanghai Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China New chiral N,S ligands with oxazoline and thiophenyl substituents at benzene ring and benzylic position have been prepared and applied in palladium catalyzed asymmetric allylic alkylation reaction to provide the product with high yield and entantioselectivity ( 82%-93% ee ).展开更多
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financially Supported by the National Natural Science Foundation of China (20772084)
文摘The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).
文摘bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China cShanghai Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China New chiral N,S ligands with oxazoline and thiophenyl substituents at benzene ring and benzylic position have been prepared and applied in palladium catalyzed asymmetric allylic alkylation reaction to provide the product with high yield and entantioselectivity ( 82%-93% ee ).
