β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid...β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.展开更多
Although trifluoromethylthiolated compounds have privileged applications in pharmaceuticals and agrochemicals,efficient strategies for the asymmetric construction of C_(sp)^(3)-SCF_(3)bonds are limited.Specifically,th...Although trifluoromethylthiolated compounds have privileged applications in pharmaceuticals and agrochemicals,efficient strategies for the asymmetric construction of C_(sp)^(3)-SCF_(3)bonds are limited.Specifically,the catalytic asymmetric nucleophilic trifluoromethylthiolation remains challenging.Here,we report a copper-catalyzed enantioselective nucleophilic trifluoromethylthiolation of secondary propargyl sulfonates with trifluoromethylthio silver.The reaction exhibits high efficiency,good enantioselectivity,high functional group tolerance,and broad substrate scope,paving a new way for the asymmetric synthesis of trifluoromethylthiolated compounds.展开更多
基金supported by the National Natural Science Foundation of China(22171206)the Natural Science Foundation of Zhejiang Province(Z23B020002,LY22B020003,)+1 种基金the Open Foundation of Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers(E22307)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2020ZD04)。
文摘β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.
基金Financial support for this work was provided by the National Natural Science Foundation of China(nos.21931013,21702225,21672238,and 21421002)the Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000).
文摘Although trifluoromethylthiolated compounds have privileged applications in pharmaceuticals and agrochemicals,efficient strategies for the asymmetric construction of C_(sp)^(3)-SCF_(3)bonds are limited.Specifically,the catalytic asymmetric nucleophilic trifluoromethylthiolation remains challenging.Here,we report a copper-catalyzed enantioselective nucleophilic trifluoromethylthiolation of secondary propargyl sulfonates with trifluoromethylthio silver.The reaction exhibits high efficiency,good enantioselectivity,high functional group tolerance,and broad substrate scope,paving a new way for the asymmetric synthesis of trifluoromethylthiolated compounds.
