The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely hea...The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely heavily on sacrificial reagents.Herein,we disclose a visible light photoredox-catalyzed 1,2-difunctionalization of terminal alkynes by using CO_(2)as an ideal quenching reagent and the xanthene dye Rhodamine 6G(Rh-6G)as a photocatalyst(PC)via consecutive photoinduced electron transfer(ConPET)process.The newly developed CO_(2)-triggered reaction provides a highly regio-and stereo-selective approach to diverse functionalized(E)-α-vinylsulfones with simultaneously efficient conversion of CO into oxalate.The practicality of this protocol is demonstrated by late-stage modification of alkynes derived from biologically active natural products or drugs.Preliminary mechanistic studies suggest that the homocoupling of CO_(2) radical anion results in the formation of oxalate.展开更多
Current methods to access aryl/alkyl thiol-substituted bicyclo[1.1.1]pentane(BCP)derivatives(valuable bioisosteres for thiophenols/thioethers)remain underdeveloped.Herein,we report a photocatalytic multicomponent reac...Current methods to access aryl/alkyl thiol-substituted bicyclo[1.1.1]pentane(BCP)derivatives(valuable bioisosteres for thiophenols/thioethers)remain underdeveloped.Herein,we report a photocatalytic multicomponent reaction via consecutive photoinduced electron transfer(ConPET)to enable simultaneous Csp3-C and Csp3-Y(Y=S,Se,Te)bond formation on[1.1.1]pentanes.This strategy delivers diverse alkyl halides(Cl,Br,I;primary,secondary,tertiary).Late-stage derivatization of drug molecules(e.g.,aspirin,methylprednisolone)and oxidations to sulfoxides/sulfones demonstrate synthetic versatility.Mechanistic studies support a radical relay pathway initiated by ConPET-mediated alkyl radical generation.The method establishes a robust platform for constructing chalcogen-rich BCP bioisosteres,addressing a critical gap in medicinal chemistry and offering significant potential for drug discovery.展开更多
α-Azaarene quaternary carbon centers are prevalent in drug molecules,making the development of efficient synthetic approaches of great interest.Herein,we describe an unprecedented method for constructingα-all-carbon...α-Azaarene quaternary carbon centers are prevalent in drug molecules,making the development of efficient synthetic approaches of great interest.Herein,we describe an unprecedented method for constructingα-all-carbon quaternary carbon-centered azaarenes by employing photocatalytic reductive coupling of various 2,2-disubstituted cycloproarylketones with readily available cyanoazaarenes.The reaction proceeds with high efficiency,displaying excellent compatibility with various functional groups and demonstrating high chemo-and regioselectivity.Mechanistic investigations suggest that consecutive photo-induced electron transfer(ConPET)plays a crucial role in the formation of photocatalyst with greater reducing capability,ultimately enabling the direct reductive conversion of unreactiveπ-bonds under mild and transition-metal-free conditions.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22471045,U2001222)the Science and Technology Planning Project of Guangdong Province(No.2021A0505030069)。
文摘The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely heavily on sacrificial reagents.Herein,we disclose a visible light photoredox-catalyzed 1,2-difunctionalization of terminal alkynes by using CO_(2)as an ideal quenching reagent and the xanthene dye Rhodamine 6G(Rh-6G)as a photocatalyst(PC)via consecutive photoinduced electron transfer(ConPET)process.The newly developed CO_(2)-triggered reaction provides a highly regio-and stereo-selective approach to diverse functionalized(E)-α-vinylsulfones with simultaneously efficient conversion of CO into oxalate.The practicality of this protocol is demonstrated by late-stage modification of alkynes derived from biologically active natural products or drugs.Preliminary mechanistic studies suggest that the homocoupling of CO_(2) radical anion results in the formation of oxalate.
基金the Natural Science Foundation of Zhejiang Province(No.LMS25B060007)the Key Research&Development Project of Science Technology Department of Zhejiang Province(No.2024C01203)for financial support.
文摘Current methods to access aryl/alkyl thiol-substituted bicyclo[1.1.1]pentane(BCP)derivatives(valuable bioisosteres for thiophenols/thioethers)remain underdeveloped.Herein,we report a photocatalytic multicomponent reaction via consecutive photoinduced electron transfer(ConPET)to enable simultaneous Csp3-C and Csp3-Y(Y=S,Se,Te)bond formation on[1.1.1]pentanes.This strategy delivers diverse alkyl halides(Cl,Br,I;primary,secondary,tertiary).Late-stage derivatization of drug molecules(e.g.,aspirin,methylprednisolone)and oxidations to sulfoxides/sulfones demonstrate synthetic versatility.Mechanistic studies support a radical relay pathway initiated by ConPET-mediated alkyl radical generation.The method establishes a robust platform for constructing chalcogen-rich BCP bioisosteres,addressing a critical gap in medicinal chemistry and offering significant potential for drug discovery.
基金Grants from the National Natural Science Foundation of China(22271077,21925103,21901062)the Natural Science Foundation of Henan(232300421078,222301420046)+2 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province(24HASTIT001)the China Postdoctoral Science Foundation(2021M690890)Henan University are gratefully acknowledged.
文摘α-Azaarene quaternary carbon centers are prevalent in drug molecules,making the development of efficient synthetic approaches of great interest.Herein,we describe an unprecedented method for constructingα-all-carbon quaternary carbon-centered azaarenes by employing photocatalytic reductive coupling of various 2,2-disubstituted cycloproarylketones with readily available cyanoazaarenes.The reaction proceeds with high efficiency,displaying excellent compatibility with various functional groups and demonstrating high chemo-and regioselectivity.Mechanistic investigations suggest that consecutive photo-induced electron transfer(ConPET)plays a crucial role in the formation of photocatalyst with greater reducing capability,ultimately enabling the direct reductive conversion of unreactiveπ-bonds under mild and transition-metal-free conditions.
