Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
Phenylseleno- and p-tolylsulfonyl substituted 1,3-dienes were conveniently prepared with high stereoselectivity by the elimination reaction of phenylseleno- and p-tolylsulfonyl substituted allyl alcohols in the presen...Phenylseleno- and p-tolylsulfonyl substituted 1,3-dienes were conveniently prepared with high stereoselectivity by the elimination reaction of phenylseleno- and p-tolylsulfonyl substituted allyl alcohols in the presence of BF3·Et2O in acetic anhydride. The products were characterized by 1H NMR, MS, IR and elemental analysis. The single crystal structure of 2a was determined by X-ray diffraction analysis.展开更多
Allylic alcohols react with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound bidentate sulfur palladium (0) complex to form 3-arylaldehydes or ketones in good yields.
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
Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in soluti...Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.展开更多
基金supported by the National Natural Science Foundation of China(No.29772007)
文摘Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
基金Project supported by the National Natural Science Foundation of China (No. 20272050).
文摘Phenylseleno- and p-tolylsulfonyl substituted 1,3-dienes were conveniently prepared with high stereoselectivity by the elimination reaction of phenylseleno- and p-tolylsulfonyl substituted allyl alcohols in the presence of BF3·Et2O in acetic anhydride. The products were characterized by 1H NMR, MS, IR and elemental analysis. The single crystal structure of 2a was determined by X-ray diffraction analysis.
文摘Allylic alcohols react with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound bidentate sulfur palladium (0) complex to form 3-arylaldehydes or ketones in good yields.
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This work was supported by the Fund for Young Scientist from the National Advanced Materials Committee of China
文摘Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.
