Developing green and practical D-labeling techniques is valuable and in high demand for medical chemistry,mechanistic studies,and materials science.Although dearomatic deuteration of simple aromatic systems represents...Developing green and practical D-labeling techniques is valuable and in high demand for medical chemistry,mechanistic studies,and materials science.Although dearomatic deuteration of simple aromatic systems represents an attractive protocol to access D-labeled compounds,the inherent chemical stability of(het)aromatics leaves successful examples rather scarce.Different from transition metal catalysis,which involves dangerous and expensive deuterium sources,and harsh reaction conditions,represented herein is the first electrophotocatalytic platform for dearomative deuteration of inert(het)arenes.Taking economical D_(2)O as the deuterium source and organic N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide)as the electrophotocatalyst,Birch-type deuteration of(het)aromatics is realized with excellent site-selectivity,good functional group compatibility,and high D-incorporation.Late-stage deuteration of complex pharmaceuticals and gram-scale scale-up are easily implemented.This methodology overcomes existing synthetic challenges,and no overreduction reaction occurs.Moreover,the electrophotocatalytic platform works well with renewable solar-to-electricity,offering an effective way to prepare synthetically useful deuterated molecules.展开更多
In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large n...In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large number of studies have demonstrated that a catalyst binds,activates,and achieves electron transfer to CO_(2).However,the formation of metal carbonyl intermediate and release of CO during the CO_(2)RR process have not received the same level of attention.Herein,three iron(Ⅱ)complexes are designed to help us to understand the activation of CO_(2)and release of CO.Our research reveals that by removing one of the axial pyridine ligands from polypyridyl-iron(Ⅱ)complex 3,the favorable H2O coordination greatly decreases the activation energy of C-O bond cleavage of complex 1 and 2,and the resultant high-spin Fe(II)carbonyl intermediate with weaker ligand field dramatically reduces CO binding affinity and improves the faradaic efficiency from∼17%to 90%in catalytic CO_(2)RR.展开更多
基金support by the National Key Research and Development Program of China(grant nos.2021YFA1500100,2022YFA1503200,and 2022YFA1502900)the National Natural Science Foundation of China(grant nos.22193013,21933007,and 22088102)+1 种基金the Strategic Priority Research Programof the Chinese Academy of Science(grant no.XDB17000000)New Cornerstone Science Foundation.
文摘Developing green and practical D-labeling techniques is valuable and in high demand for medical chemistry,mechanistic studies,and materials science.Although dearomatic deuteration of simple aromatic systems represents an attractive protocol to access D-labeled compounds,the inherent chemical stability of(het)aromatics leaves successful examples rather scarce.Different from transition metal catalysis,which involves dangerous and expensive deuterium sources,and harsh reaction conditions,represented herein is the first electrophotocatalytic platform for dearomative deuteration of inert(het)arenes.Taking economical D_(2)O as the deuterium source and organic N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide)as the electrophotocatalyst,Birch-type deuteration of(het)aromatics is realized with excellent site-selectivity,good functional group compatibility,and high D-incorporation.Late-stage deuteration of complex pharmaceuticals and gram-scale scale-up are easily implemented.This methodology overcomes existing synthetic challenges,and no overreduction reaction occurs.Moreover,the electrophotocatalytic platform works well with renewable solar-to-electricity,offering an effective way to prepare synthetically useful deuterated molecules.
基金supported by the National Key R&D Program of China(grant nos.2022YFA1502900,2022YFA0911900,and 2021YFA1500800)the National Natural Science Foundation of China(grant nos.22231001,21933007,22193013,and 22088102)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Science(grant no.XDB17000000)the New Cornerstone Science Foundation.
文摘In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large number of studies have demonstrated that a catalyst binds,activates,and achieves electron transfer to CO_(2).However,the formation of metal carbonyl intermediate and release of CO during the CO_(2)RR process have not received the same level of attention.Herein,three iron(Ⅱ)complexes are designed to help us to understand the activation of CO_(2)and release of CO.Our research reveals that by removing one of the axial pyridine ligands from polypyridyl-iron(Ⅱ)complex 3,the favorable H2O coordination greatly decreases the activation energy of C-O bond cleavage of complex 1 and 2,and the resultant high-spin Fe(II)carbonyl intermediate with weaker ligand field dramatically reduces CO binding affinity and improves the faradaic efficiency from∼17%to 90%in catalytic CO_(2)RR.
