Vapor phase catalytic hydrogen peroxide production by oxidation of water is possible by coupling the reaction with oxidation of an organic sacrificial reductant. It is potentially a safer process than direct synthesis...Vapor phase catalytic hydrogen peroxide production by oxidation of water is possible by coupling the reaction with oxidation of an organic sacrificial reductant. It is potentially a safer process than direct synthesis from H2 and O2. Based on mechanistic information available mostly for liquid phase catalytic processes, feasible reaction mechanisms for such coupled reactions are proposed based on which desirable catalyst properties are identified. It is found that the surface-adsorbed oxygen bond is an important parameter for identifying desirable catalysts. Thermodynamics can be used to identify the types of organic oxidation reactions that can couple with water oxidation such that H2O2 formation becomes thermodynamically favorable. Reactions such as epoxidation of alkenes and selective oxidation of alkanes to alcohols cannot provide sufficient thermodynamic driving force, whereas oxidation of alcohols to aldehydes and to acids can. Finally, further research is suggested to identify catalytic properties important for H2O2 decomposition and for coupling selective oxidation of organic compounds to oxidation of H2O in order to facilitate development of H2O2 production coupled with selective organic oxidation.展开更多
The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the sco...The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the scopes of arenes are usually suitable for elec-tron-deficient heterocyclic compounds,rather than electron-rich arenes.Herein,we report an electrooxidation-induced alkylation of electron-rich arenes with H_(2) evolution under exogenous oxidant-free conditions,avoiding the utilization of metal catalysts.This pro-tocol is well performed with various electron-rich aniline derivatives and nitrogen-containing heterocyclic compounds.We anticipate that this electro-oxidative C(sp^(3))-H arylation represents an important expansion for the classic arenes alkylation,thereby proving an attractive strategy for the developments of radical cross-coupling chemistry.展开更多
Silica gel was soaked with 2 naphthol and FeCl 3 (10∶1, molar ratio) dissolved in acetone, and the mixture was evaporated in vacuum at 30 ℃. Using air as oxidant reagent, oxidative coupling reaction of 2 naphthol gi...Silica gel was soaked with 2 naphthol and FeCl 3 (10∶1, molar ratio) dissolved in acetone, and the mixture was evaporated in vacuum at 30 ℃. Using air as oxidant reagent, oxidative coupling reaction of 2 naphthol gives 84% yield of (±)2, 2′ dihydroxy 1, 1′ binaphthyl.展开更多
基金support by Northwestern University through a gift from Dr.Warren Haug is greatly appreciated
文摘Vapor phase catalytic hydrogen peroxide production by oxidation of water is possible by coupling the reaction with oxidation of an organic sacrificial reductant. It is potentially a safer process than direct synthesis from H2 and O2. Based on mechanistic information available mostly for liquid phase catalytic processes, feasible reaction mechanisms for such coupled reactions are proposed based on which desirable catalyst properties are identified. It is found that the surface-adsorbed oxygen bond is an important parameter for identifying desirable catalysts. Thermodynamics can be used to identify the types of organic oxidation reactions that can couple with water oxidation such that H2O2 formation becomes thermodynamically favorable. Reactions such as epoxidation of alkenes and selective oxidation of alkanes to alcohols cannot provide sufficient thermodynamic driving force, whereas oxidation of alcohols to aldehydes and to acids can. Finally, further research is suggested to identify catalytic properties important for H2O2 decomposition and for coupling selective oxidation of organic compounds to oxidation of H2O in order to facilitate development of H2O2 production coupled with selective organic oxidation.
基金the National Key R&D Program of China(No.2021YFA1500104)the National Natural Science Foundation of China(No.22031008)the Science Foundation of Wuhan(No.2020010601012192)。
文摘The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the scopes of arenes are usually suitable for elec-tron-deficient heterocyclic compounds,rather than electron-rich arenes.Herein,we report an electrooxidation-induced alkylation of electron-rich arenes with H_(2) evolution under exogenous oxidant-free conditions,avoiding the utilization of metal catalysts.This pro-tocol is well performed with various electron-rich aniline derivatives and nitrogen-containing heterocyclic compounds.We anticipate that this electro-oxidative C(sp^(3))-H arylation represents an important expansion for the classic arenes alkylation,thereby proving an attractive strategy for the developments of radical cross-coupling chemistry.
文摘Silica gel was soaked with 2 naphthol and FeCl 3 (10∶1, molar ratio) dissolved in acetone, and the mixture was evaporated in vacuum at 30 ℃. Using air as oxidant reagent, oxidative coupling reaction of 2 naphthol gives 84% yield of (±)2, 2′ dihydroxy 1, 1′ binaphthyl.
