α-Nitroketones represent an important class of organic compounds in synthetic chemistry because of the synergistic interaction between their adjacent carbonyl and nitro functional groups.However,current reporting met...α-Nitroketones represent an important class of organic compounds in synthetic chemistry because of the synergistic interaction between their adjacent carbonyl and nitro functional groups.However,current reporting methods often pose environmental concerns and require harsh reaction conditions,such as the use of noble metal catalysts and external oxidants.Herein,we report a novel and environmentally benign electrochemical bifunctional groups strategy for the efficient synthesis ofα-nitroketones directly from olefins.This approach is based on a dual-source system,in which Fe(NO_(3))_(3)·9H_(2)O serves as a versatile precursor,simultaneously supplying the nitro group,while trace amounts of water inherently present in the electrolyte act as the oxygen source for carbonyl formation.This tandem oxidation-nitration process enables the direct construction of the valuableα-nitroketone scaffold from simple starting materials in a single operational step.A primary advantage of this methodology lies in its inherently green and sustainable nature.Compared with conventional methods,this strategy markedly decreases the necessity of using hazardous and volatile nitromethane as a nitro source and avoids the routine application of stoichiometric condensation or oxidizing agents that tend to produce large quantities of chemical waste.Instead,electricity functions as a traceless redox agent,driving the transformation under mild conditions-generally at room temperature or with minimal heating and under ambient pressure.This leads to a significantly reduced environmental footprint and enhances operational safety.The reaction demonstrates remarkable synthetic utility,characterized by a broad substrate scope.A wide variety of olefins,including those bearing aryl,aliphatic,and heterocyclic substituents,are smoothly converted into the correspondingα-nitroketones in moderate to good yields.In summary,we have developed a mild,efficient,and sustainable electrochemical route toα-nitroketones.By integrating atom-economic principles with the advantages of electrosynthesis-including inherent safety and scalability-this work provides a powerful and practical alternative to conventional methods,aligning with the growing demands of modern green chemistry.展开更多
Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)ca...Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.展开更多
基金supported by the Guangxi Science and Technology Base and Talent Project(High level Innovative Talents and Team Training)(Guike AD23026094)the National Natural Science Foundation of China(22161008)+3 种基金the Postdoctoral Fellowship Program of CPSF(GZB20250265)the Postdoctoral Science Foundation of China(2024MD763943)the Project for Enhancing Young and Middle-aged Teacher's Research Basis Ability in Colleges of Guangxi(2025KY0095)the Guangxi Young Elite Scientist Sponsorship Program(GXYESS2025057).
文摘α-Nitroketones represent an important class of organic compounds in synthetic chemistry because of the synergistic interaction between their adjacent carbonyl and nitro functional groups.However,current reporting methods often pose environmental concerns and require harsh reaction conditions,such as the use of noble metal catalysts and external oxidants.Herein,we report a novel and environmentally benign electrochemical bifunctional groups strategy for the efficient synthesis ofα-nitroketones directly from olefins.This approach is based on a dual-source system,in which Fe(NO_(3))_(3)·9H_(2)O serves as a versatile precursor,simultaneously supplying the nitro group,while trace amounts of water inherently present in the electrolyte act as the oxygen source for carbonyl formation.This tandem oxidation-nitration process enables the direct construction of the valuableα-nitroketone scaffold from simple starting materials in a single operational step.A primary advantage of this methodology lies in its inherently green and sustainable nature.Compared with conventional methods,this strategy markedly decreases the necessity of using hazardous and volatile nitromethane as a nitro source and avoids the routine application of stoichiometric condensation or oxidizing agents that tend to produce large quantities of chemical waste.Instead,electricity functions as a traceless redox agent,driving the transformation under mild conditions-generally at room temperature or with minimal heating and under ambient pressure.This leads to a significantly reduced environmental footprint and enhances operational safety.The reaction demonstrates remarkable synthetic utility,characterized by a broad substrate scope.A wide variety of olefins,including those bearing aryl,aliphatic,and heterocyclic substituents,are smoothly converted into the correspondingα-nitroketones in moderate to good yields.In summary,we have developed a mild,efficient,and sustainable electrochemical route toα-nitroketones.By integrating atom-economic principles with the advantages of electrosynthesis-including inherent safety and scalability-this work provides a powerful and practical alternative to conventional methods,aligning with the growing demands of modern green chemistry.
基金supported by the Guangxi Science and Technology Major Program(Guike AA24263012)the National Natural Science Foundation of China(22471046,22301048,22201049)the Bagui Outstanding Youth Talent Project。
文摘Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.
