Herein,we report an efficient and practical protocol for the photoinduced dehalocyclization of ortho-halophenylacrylamides with formate by the engagement of a CO_(2) radical anion to access substituted oxindoles.This ...Herein,we report an efficient and practical protocol for the photoinduced dehalocyclization of ortho-halophenylacrylamides with formate by the engagement of a CO_(2) radical anion to access substituted oxindoles.This method proceeds smoothly under mild conditions and exhibits a wide range of substrate as well as remarkable functional group compatibility.展开更多
An efficient decarboxylative/defluorinative alkylation for synthesizing gem-difluoroalkenes is described,providing a general method for installation of the challenging alkyl fragments containing a-electron-withdrawing...An efficient decarboxylative/defluorinative alkylation for synthesizing gem-difluoroalkenes is described,providing a general method for installation of the challenging alkyl fragments containing a-electron-withdrawing groups into a-trifluoromethyl alkenes.Mechanistic studies suggest that this process involves an SN2,-type synthetic route in the absence of transition-metal catalysts or photocatalysis.Moreover,this protocol can easily be scaled up,and successfully applied to the modification of biologically active molecules,thus complementing methodologies that give access to structurally versatile gem-difluoroalkenes.展开更多
A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition t...A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition to unsaturated bond followed by intramolecular addition to arene, with a broad scope of N-hydroxyphthalimide derived redox active esters under visible light irradiation. The reactions are suggested to proceed through photoactivation of a transiently assembled chromophore from electron-deficient phthalimide moiety and iodide anion through an anion-π interaction in solvent cage followed by diffusion to generate solvated free radical species to react with C-H substrates. The simplicity, practicality, and broad substrate scope of this method highlight the synthetic power of photocatalysis through transiently assembled chromophore, and will hopefully inspire further developments of low cost photocatalysis based on various non-covalent interactions, which are prevalent in supramolecular chemistry and biosystems, for sustainable organic synthesis.展开更多
基金supported by the National Natural Science Foundation of China(No.22293011).
文摘Herein,we report an efficient and practical protocol for the photoinduced dehalocyclization of ortho-halophenylacrylamides with formate by the engagement of a CO_(2) radical anion to access substituted oxindoles.This method proceeds smoothly under mild conditions and exhibits a wide range of substrate as well as remarkable functional group compatibility.
基金the support from the National Natural Science Foundation of China(Nos.21732006,51821006 and 51961135104)the Natural Science Foundation of Anhui(No.2008085MB40)+1 种基金the USTC Research Funds of the Double First Class Initiative(No.YD2060002003)The authors thank Xi Lu(University of Science and Technology of China)for insightful discussion during the preparation of the manuscript.
文摘An efficient decarboxylative/defluorinative alkylation for synthesizing gem-difluoroalkenes is described,providing a general method for installation of the challenging alkyl fragments containing a-electron-withdrawing groups into a-trifluoromethyl alkenes.Mechanistic studies suggest that this process involves an SN2,-type synthetic route in the absence of transition-metal catalysts or photocatalysis.Moreover,this protocol can easily be scaled up,and successfully applied to the modification of biologically active molecules,thus complementing methodologies that give access to structurally versatile gem-difluoroalkenes.
基金supported by the National Natural Science Foundation of China(GG2065010002)and KY(2060000119)support from the Fundamental Research Funds for the Central Universities(WK2060120003)Anhui Provincial Natural Science Foundation(1908085QB53)。
文摘A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition to unsaturated bond followed by intramolecular addition to arene, with a broad scope of N-hydroxyphthalimide derived redox active esters under visible light irradiation. The reactions are suggested to proceed through photoactivation of a transiently assembled chromophore from electron-deficient phthalimide moiety and iodide anion through an anion-π interaction in solvent cage followed by diffusion to generate solvated free radical species to react with C-H substrates. The simplicity, practicality, and broad substrate scope of this method highlight the synthetic power of photocatalysis through transiently assembled chromophore, and will hopefully inspire further developments of low cost photocatalysis based on various non-covalent interactions, which are prevalent in supramolecular chemistry and biosystems, for sustainable organic synthesis.
