Acceleration Effects of Phosphine Ligands on the Rhodium-Catalyzed Dehydrogenative Silylation and Germylation of Unactivated C(sp3)–H Bonds

作者: Masahito Murai , Hirotaka Takeshima , Haruka Morita , Yoichiro Kuninobu , Kazuhiko Takai

DOI: 10.1021/ACS.JOC.5B00920

关键词: PhotochemistryMedicinal chemistryChemistryLigandSteric effectsBite angleDesymmetrizationEnantioselective synthesisPhosphineSilylationReactivity (chemistry)

摘要: The current work describes the marked rate of acceleration caused by phosphine ligands on rhodium-catalyzed dehydrogenative silylation and germylation unactivated C(sp3)–H bonds. reactivity was affected steric electronic nature ligands. use bulky electron-rich diphosphine ligand (R)-DTBM-SEGPHOS highly effective to yield products selectively in presence a hydrogen acceptor. An appropriate choice C2-symmetric chiral enables asymmetric via enantioselective desymmetrization bond. unprecedented catalytic bonds with dehydrogenation also examined combination rhodium complex wide bite angle provide corresponding 2,3-dihydrobenzo[b]germoles good yield.

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