Difunctionalization of alkynes represents a powerful and straightforward approach to the synthesis of complex molecules.However,the radical difunctionalization of alkynes mediated by bifunctional reagents remains chal...Difunctionalization of alkynes represents a powerful and straightforward approach to the synthesis of complex molecules.However,the radical difunctionalization of alkynes mediated by bifunctional reagents remains challenging and underexplored,despite significant progress having been made in alkene difunctionalization.Here,we report a novel arylsulfonylacetate skeleton in which aryl rings are attached to acetates through SO_(2),serving as a powerful bifunctional reagent for the alkylarylation of alkynes via vinyl-radical intermediate under photoredox conditions.This modular bifunctional reagent enables the simultaneous incorporation of a wide range of functional groups,including(hetero)aryl ring and alkyl carboxylate into alkynes,resulting in synthetically valuable all-carbon tetrasubstituted alkene derivatives.This transformation is distinguished by its redox-neutral nature,readily accessible starting materials,compatibility with diverse functional groups and its capacity to facilitate convergent synthesis.The utility of this approach was further demonstrated by the late-stage functionalization of complex molecules and the preparation of fluorescent molecules and anti-cancer drugs.展开更多
Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhance...Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhanced efficiency and structural variability,which is in high demand for atom-economic and sustainable synthesis.Among them,bifunctional reagents containing Nheteroaryl groups have received much attention due to their ability to introduce privileged N-heteroaryl moieties into complex molecules that are otherwise challenging to access.Furthermore,these reagents have been employed under visible-light conditions to achieve various synthetic applications,enabling difunctionalization of alkenes,alkynes,and[1.1.1]propellanes under mild reaction conditions,providing access to highly functionalized N-heteroarenes.In this review,we provide an overview of the recent achievements and applications of photoinduced difunctionalization using bifunctional reagents containing N-heteroaryl groups.We systematically categorize the representative contributions in the field based on bifunctional reagents and their reactivity patterns.This review aims to highlight the potential of these reagents as powerful synthetic tools for sustainable and diverse synthesis.展开更多
The cyclizaion reactions of Lawesson's reagent(LR) with the substrates containing two functional groups such as hydroxy groups,amino groups, has been applied to prepare the O-P-O,N-P-N type 5-membered and 6-member...The cyclizaion reactions of Lawesson's reagent(LR) with the substrates containing two functional groups such as hydroxy groups,amino groups, has been applied to prepare the O-P-O,N-P-N type 5-membered and 6-membered phosphorus heterocycles.The heterocyclizaional possibility of LR with bifunctional compounds was also discussed.展开更多
基金supported by the National Natural Science Foundation of China(21901199)Xi’an Jiaotong University(7121192002)。
文摘Difunctionalization of alkynes represents a powerful and straightforward approach to the synthesis of complex molecules.However,the radical difunctionalization of alkynes mediated by bifunctional reagents remains challenging and underexplored,despite significant progress having been made in alkene difunctionalization.Here,we report a novel arylsulfonylacetate skeleton in which aryl rings are attached to acetates through SO_(2),serving as a powerful bifunctional reagent for the alkylarylation of alkynes via vinyl-radical intermediate under photoredox conditions.This modular bifunctional reagent enables the simultaneous incorporation of a wide range of functional groups,including(hetero)aryl ring and alkyl carboxylate into alkynes,resulting in synthetically valuable all-carbon tetrasubstituted alkene derivatives.This transformation is distinguished by its redox-neutral nature,readily accessible starting materials,compatibility with diverse functional groups and its capacity to facilitate convergent synthesis.The utility of this approach was further demonstrated by the late-stage functionalization of complex molecules and the preparation of fluorescent molecules and anti-cancer drugs.
基金supported by the Institute for Basic Science(IBS-R010-A2)。
文摘Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhanced efficiency and structural variability,which is in high demand for atom-economic and sustainable synthesis.Among them,bifunctional reagents containing Nheteroaryl groups have received much attention due to their ability to introduce privileged N-heteroaryl moieties into complex molecules that are otherwise challenging to access.Furthermore,these reagents have been employed under visible-light conditions to achieve various synthetic applications,enabling difunctionalization of alkenes,alkynes,and[1.1.1]propellanes under mild reaction conditions,providing access to highly functionalized N-heteroarenes.In this review,we provide an overview of the recent achievements and applications of photoinduced difunctionalization using bifunctional reagents containing N-heteroaryl groups.We systematically categorize the representative contributions in the field based on bifunctional reagents and their reactivity patterns.This review aims to highlight the potential of these reagents as powerful synthetic tools for sustainable and diverse synthesis.
文摘The cyclizaion reactions of Lawesson's reagent(LR) with the substrates containing two functional groups such as hydroxy groups,amino groups, has been applied to prepare the O-P-O,N-P-N type 5-membered and 6-membered phosphorus heterocycles.The heterocyclizaional possibility of LR with bifunctional compounds was also discussed.
