An innovative visible-light-driven direct hydrogen atom transfer(d-HAT)of Ge–H bond has been developed,wherein the photoexcited 9,10-phenanthraquinone(PCHAT9)serves as an efficient photocatalyst for the generation of...An innovative visible-light-driven direct hydrogen atom transfer(d-HAT)of Ge–H bond has been developed,wherein the photoexcited 9,10-phenanthraquinone(PCHAT9)serves as an efficient photocatalyst for the generation of germanium-centered radicals from germanium hydrides including Ph3GeH,nBu3GeH,and Ph2GeH2.By employing hypervalent iodine reagents as SOMOphiles,this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed byβ-cleavage of a carboxyl radical to yield a diverse array of ethynyl-,vinyl-,nitrile-,and phenyl-functionalized germanes.The methodological leap signifies a noteworthy departure from the previous photocatalytic indirect hydrogen atom transfer(i-HAT)relying on combined usage of PCSET with abstractors,which not only advances the methodology for creating germanium radicals in a photocatalytic fashion but also provides access to structurally novel and pharmaceutically promising organogermanium compounds that are difficult to synthesize by routine methods.展开更多
The C–Ge cross-coupling offers a promising approach for the precise synthesis of organogermanes. However, the current methods are primarily effective in the germylation of organo(pseudo)halides. This work demonstrate...The C–Ge cross-coupling offers a promising approach for the precise synthesis of organogermanes. However, the current methods are primarily effective in the germylation of organo(pseudo)halides. This work demonstrates the possibility of transferring low-cost and easily available ester groups into organogermanes through the cleavage of stable C–O bonds. Primary,secondary, and even tertiary benzylic pivalates were coupled well with chlorogermanes. The reactions proceed under mild conditions. The scalability of this reaction and derivatization of the formed benzylgermanes are demonstrated.展开更多
基金supported by the National Key R&D Program of China(2021YFB4001100,2021YFB4001101)the National Natural Science Foundation of China(22071222 and 22171249)+4 种基金the Science&Technology Innovation Talents in Universities of Henan Province(23HASTIT003)the Key Research Projects of Universities in Henan Province(23A150054)Natural Science Foundation of Henan Province(232300421363,242300420185)the Key Scientific and Technological Project of Henan Province(232102230140)the Doctor Foundation of Henan University of Engineering(D2022004).
文摘An innovative visible-light-driven direct hydrogen atom transfer(d-HAT)of Ge–H bond has been developed,wherein the photoexcited 9,10-phenanthraquinone(PCHAT9)serves as an efficient photocatalyst for the generation of germanium-centered radicals from germanium hydrides including Ph3GeH,nBu3GeH,and Ph2GeH2.By employing hypervalent iodine reagents as SOMOphiles,this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed byβ-cleavage of a carboxyl radical to yield a diverse array of ethynyl-,vinyl-,nitrile-,and phenyl-functionalized germanes.The methodological leap signifies a noteworthy departure from the previous photocatalytic indirect hydrogen atom transfer(i-HAT)relying on combined usage of PCSET with abstractors,which not only advances the methodology for creating germanium radicals in a photocatalytic fashion but also provides access to structurally novel and pharmaceutically promising organogermanium compounds that are difficult to synthesize by routine methods.
基金supported by the National Natural Science Foundation of China (22071084, 22271127)the Fundamental Research Funds for the Central Universities (lzujbky-2022-ey01)。
文摘The C–Ge cross-coupling offers a promising approach for the precise synthesis of organogermanes. However, the current methods are primarily effective in the germylation of organo(pseudo)halides. This work demonstrates the possibility of transferring low-cost and easily available ester groups into organogermanes through the cleavage of stable C–O bonds. Primary,secondary, and even tertiary benzylic pivalates were coupled well with chlorogermanes. The reactions proceed under mild conditions. The scalability of this reaction and derivatization of the formed benzylgermanes are demonstrated.
