Herein lies a convenient and highly efficient method of olefin isomerization in the presence of RuCl3？3H2O in ionic liquid（IL）. More importantly, RuCl3？3H2O is a robust and recyclable catalyst. Nine cycles of RuCl...Herein lies a convenient and highly efficient method of olefin isomerization in the presence of RuCl3？3H2O in ionic liquid（IL）. More importantly, RuCl3？3H2O is a robust and recyclable catalyst. Nine cycles of RuCl3？3H2O as the catalyst were performed for the isomerization reactions of the selected substrate in IL and MeOH.展开更多
Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins.However,the synthesis of optically active all-carbon quaternary stereocenters v...Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins.However,the synthesis of optically active all-carbon quaternary stereocenters via this strategy is still rare.Herein,we report a cobaltcatalyzed desymmetric olefin isomerization to access 1-methylcyclohexenes bearingβ-quaternary stereocenters in a chemo-,site-,and stereoselective fashion.Preliminary mechanistic studies have revealed the Co-H insertion/β–Helimination reaction pathway and the origin of remote stereocontrol of all-carbon quaternary centers.The gram-scale synthesis and stereoretentive transformations of spirocyclic products demonstrate the synthetic utility of this reaction.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.21072149, 20872108)
文摘Herein lies a convenient and highly efficient method of olefin isomerization in the presence of RuCl3？3H2O in ionic liquid（IL）. More importantly, RuCl3？3H2O is a robust and recyclable catalyst. Nine cycles of RuCl3？3H2O as the catalyst were performed for the isomerization reactions of the selected substrate in IL and MeOH.
基金We gratefully acknowledge funding from the National Key R&D Program of China(grant no.2021YFF0701600)the National Natural Science Foundation of China(grant nos.22171159 and 22225103).
文摘Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins.However,the synthesis of optically active all-carbon quaternary stereocenters via this strategy is still rare.Herein,we report a cobaltcatalyzed desymmetric olefin isomerization to access 1-methylcyclohexenes bearingβ-quaternary stereocenters in a chemo-,site-,and stereoselective fashion.Preliminary mechanistic studies have revealed the Co-H insertion/β–Helimination reaction pathway and the origin of remote stereocontrol of all-carbon quaternary centers.The gram-scale synthesis and stereoretentive transformations of spirocyclic products demonstrate the synthetic utility of this reaction.
