We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT ca...We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT catalyst could act as a nucleophile to generate primary radicals via an S_(N)2 pathway.However,this reaction was limited to benzyl radicals.Herein,we reported a new catalytic property of the MPT catalyst.The photoexcited MPT catalyst(E(MPT^(+)/MPT^(*))=-1.60 V vs.Ag/AgCl in MeCN)could reduce NHPI esters through a single electron transfer process.Various carbon radicals,including benzyl radical,as well as primary,secondary and tertiary alkyl radicals,could be generated easily.Notably,amino acids,peptide,pharmaceuticals,and other biologically active mole cules could be modified by using this methodology showing the potential synthetic utility of this method.展开更多
基金supported by the National Natural Science Foundation of China(22102160)the"CUG Scholar"Scientific Research Funds at China University of Geosciences(Wuhan)(Project No.2022014)+1 种基金the Wuhan Talent Plan(Excellent Young Talents,No.20230350051)the Zhejiang Provincial Natural Science Foundation of China(No.LQ22B020004).
文摘We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT catalyst could act as a nucleophile to generate primary radicals via an S_(N)2 pathway.However,this reaction was limited to benzyl radicals.Herein,we reported a new catalytic property of the MPT catalyst.The photoexcited MPT catalyst(E(MPT^(+)/MPT^(*))=-1.60 V vs.Ag/AgCl in MeCN)could reduce NHPI esters through a single electron transfer process.Various carbon radicals,including benzyl radical,as well as primary,secondary and tertiary alkyl radicals,could be generated easily.Notably,amino acids,peptide,pharmaceuticals,and other biologically active mole cules could be modified by using this methodology showing the potential synthetic utility of this method.
