Terminal monohaloalkenes are common synthetic fragments used in organic synthesis and are also found in many natural products.Their Z/E stereoisomers are difficult to physically separate,being a persistent difficulty ...Terminal monohaloalkenes are common synthetic fragments used in organic synthesis and are also found in many natural products.Their Z/E stereoisomers are difficult to physically separate,being a persistent difficulty for functional molecular design and synthesis.Herein,we report complementary hydride and hydrogen radical generation pathways to effectuate hydrodehalogenation and deuterodehalogenation of gem-dihaloalkenes,producing stereo-defined deuterated or nondeuterated(Z)-and(E)-terminal monofluoroalkenes and(E)-terminal monochloroalkenes.Our methods have broad substrate scopes and good functional group tolerance.Mechanistic studies and density functional theory calculations elucidate the stereoselectivity.展开更多
Deuterium(D)-labelled organic compounds are used in many applications e.g,as thempeutic agents,intemal standards in drug discovery and development,and new functional materials including dyes,catalysts,and light emitte...Deuterium(D)-labelled organic compounds are used in many applications e.g,as thempeutic agents,intemal standards in drug discovery and development,and new functional materials including dyes,catalysts,and light emitters.Conventionally,the synthesis of D-labelled compounds relies on(bio)catalysts due to their regio-and stereoselectivity,mild reaction conditions,and treatment of a broad scope of substrates.However,most(bio)catalysts are expensive to prepare/isolate,and some contain precious metals(PMs),e.g,Ir,Pd,whose markets are unpredictable,and which need to be separated from the products at great expense,postreaction.With the geneml shift away from traditional‘make-use-dispose’approaches to ones that are less wasteful,the use of recyclable catalysts in both batch and continuous flow systems are increasingly employed.In this work,we comprehensively and critically review the catalysts and immobilization and recycling strategies implemented for the preparation of D-labelled organic compounds.Our aim is to highlight the most effective advances and expose the gaps in the literature to in form future research.展开更多
基金support from the National Natural Science Foundation of China(grant nos.22293011 and 22371273)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(grant no.2023476)+1 种基金the National Science Foundation of Anhui Province(grant no.2208085J26)the New Cornerstone Science Foundation through the XPLORER PRIZE.
文摘Terminal monohaloalkenes are common synthetic fragments used in organic synthesis and are also found in many natural products.Their Z/E stereoisomers are difficult to physically separate,being a persistent difficulty for functional molecular design and synthesis.Herein,we report complementary hydride and hydrogen radical generation pathways to effectuate hydrodehalogenation and deuterodehalogenation of gem-dihaloalkenes,producing stereo-defined deuterated or nondeuterated(Z)-and(E)-terminal monofluoroalkenes and(E)-terminal monochloroalkenes.Our methods have broad substrate scopes and good functional group tolerance.Mechanistic studies and density functional theory calculations elucidate the stereoselectivity.
基金the European Union's Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie Grant Agreement No.945380Financial support from the Slove-nian Research and Innovation Agency(Research Core Funding Grant No.P1-0230,project No.J1-3018 and J7-50041)is also gntcfully acknowledged.F.P.received funding under the ERASMUS+Programme(E10184018)。
文摘Deuterium(D)-labelled organic compounds are used in many applications e.g,as thempeutic agents,intemal standards in drug discovery and development,and new functional materials including dyes,catalysts,and light emitters.Conventionally,the synthesis of D-labelled compounds relies on(bio)catalysts due to their regio-and stereoselectivity,mild reaction conditions,and treatment of a broad scope of substrates.However,most(bio)catalysts are expensive to prepare/isolate,and some contain precious metals(PMs),e.g,Ir,Pd,whose markets are unpredictable,and which need to be separated from the products at great expense,postreaction.With the geneml shift away from traditional‘make-use-dispose’approaches to ones that are less wasteful,the use of recyclable catalysts in both batch and continuous flow systems are increasingly employed.In this work,we comprehensively and critically review the catalysts and immobilization and recycling strategies implemented for the preparation of D-labelled organic compounds.Our aim is to highlight the most effective advances and expose the gaps in the literature to in form future research.
