Chlorine-substituted ketones are crucial intermediates in organic synthesis,and acyl chlorination of chemical feedstocks employing commercially available benzoyl chloride provides an atom-and-step economic route for t...Chlorine-substituted ketones are crucial intermediates in organic synthesis,and acyl chlorination of chemical feedstocks employing commercially available benzoyl chloride provides an atom-and-step economic route for their synthesis.While atomtransfer radical addition(ATRA)has proven effective for 1,2-acyl chlorination,the efficient realization of 1,3-acyl chlorination has remained a considerable challenge.In this study,an NHC/photocatalyst dual-catalyzed system was developed to facilitate the 1,3-acyl chlorination of cyclopropanes using benzoyl chloride as a bifunctional reagent.This strategy also enables the synthesis of acyl-cyclopropanes with quaternary carbon centers through a nucleophilic annulation process.The practical utility of this approach was demonstrated through large-scale synthesis,product derivatization,and the preparation of analogs of antipsychotics,including haloperidol,melperone and fluanisone.展开更多
基金supported by the National Key R&D Program of China(2024YFA1509704)the National Natural Science Foundation of China(22471034,22193012,22201033)+1 种基金the Natural Science Foundation of Jilin Province(20230101047JC,YDZJ202201ZYTS338)the Fundamental Research Funds for the Central Universities。
文摘Chlorine-substituted ketones are crucial intermediates in organic synthesis,and acyl chlorination of chemical feedstocks employing commercially available benzoyl chloride provides an atom-and-step economic route for their synthesis.While atomtransfer radical addition(ATRA)has proven effective for 1,2-acyl chlorination,the efficient realization of 1,3-acyl chlorination has remained a considerable challenge.In this study,an NHC/photocatalyst dual-catalyzed system was developed to facilitate the 1,3-acyl chlorination of cyclopropanes using benzoyl chloride as a bifunctional reagent.This strategy also enables the synthesis of acyl-cyclopropanes with quaternary carbon centers through a nucleophilic annulation process.The practical utility of this approach was demonstrated through large-scale synthesis,product derivatization,and the preparation of analogs of antipsychotics,including haloperidol,melperone and fluanisone.
