The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylatio...The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.展开更多
Organogermanium compounds have exhibited great application potential in the fields of synthetic chemistry,materials science,and medicinal chemistry due to their unique chemical,physical,and biological properties.In th...Organogermanium compounds have exhibited great application potential in the fields of synthetic chemistry,materials science,and medicinal chemistry due to their unique chemical,physical,and biological properties.In this regard,the development of effective methods for the synthesis of these compounds has attracted increased attention.Among various approaches,hydrogermylation of unsaturated carbon-carbon bonds stands out for its directness and atom economy.However,catalytic asymmetric hydrogermylation methods to assemble diverse chiral germanes remain a challenge to chemical synthesis.Herein,we report the development of a Cu-catalyzed asymmetric intermolecular hydrogermylation of simple activated alkenes with hydrogermanes,which allows for the efficient and straightforward construction of enantioenriched carbon-and germaniumstereogenic germanes in decent yields with good to excellent enantioselectivities under mild conditions.Central to the success is the ligand-steered in-situ generation of a key[Cu-Ge]species,followed by the enantioselective insertion of alkenes,delivering chiral organogermanes with precise chemo-,regio-,and stereocontrol.This facile and convenient approach towards versatile chiral germane platform molecules promises to unlock novel applications across a range of fields.展开更多
Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This pape...Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This paper reviews the advances in transition-metal-catalyzed hydrogermylation of unsaturated carbon-carbon bonds,including alkenes,alkynes,dienes,and allenes,with the objective of providing readers with the status of the field.Progress,problems,and perspectives in this field are discussed.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22201049,22471046)the Ba-Gui Youth Top-notch Talents Project of Guangxithe National HighLevel Personnel of Special Support Program for Young Top-notch Talents(9th batch)。
文摘The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.
基金support from the National Natural Science Foundation of China(grant nos.22122102,22101120,22271134,and 22203070)Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002)+1 种基金Guangdong Pearl River Talent Program(grant no.2019QN01Y628)Shenzhen Science and Technology Innovation Committee(grant nos.RCJC20221008092723013 and JCYJ20230807093104009).
文摘Organogermanium compounds have exhibited great application potential in the fields of synthetic chemistry,materials science,and medicinal chemistry due to their unique chemical,physical,and biological properties.In this regard,the development of effective methods for the synthesis of these compounds has attracted increased attention.Among various approaches,hydrogermylation of unsaturated carbon-carbon bonds stands out for its directness and atom economy.However,catalytic asymmetric hydrogermylation methods to assemble diverse chiral germanes remain a challenge to chemical synthesis.Herein,we report the development of a Cu-catalyzed asymmetric intermolecular hydrogermylation of simple activated alkenes with hydrogermanes,which allows for the efficient and straightforward construction of enantioenriched carbon-and germaniumstereogenic germanes in decent yields with good to excellent enantioselectivities under mild conditions.Central to the success is the ligand-steered in-situ generation of a key[Cu-Ge]species,followed by the enantioselective insertion of alkenes,delivering chiral organogermanes with precise chemo-,regio-,and stereocontrol.This facile and convenient approach towards versatile chiral germane platform molecules promises to unlock novel applications across a range of fields.
基金supported by the National Key Research and Development Program of the Ministry of Science and Technology of China(2021YFA1500203)Natural Science Foundation of China(22201290,22061160464,and 21821002)Shanghai Sailing Program(22YF1458200).
文摘Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This paper reviews the advances in transition-metal-catalyzed hydrogermylation of unsaturated carbon-carbon bonds,including alkenes,alkynes,dienes,and allenes,with the objective of providing readers with the status of the field.Progress,problems,and perspectives in this field are discussed.
