Switch of Regioselectivity in Palladium-Catalyzed Silaboration of Terminal Alkynes by Ligand-Dependent Control of Reductive Elimination
作者： Toshimichi Ohmura , Kazuyuki Oshima , Hiroki Taniguchi , Michinori Suginome
DOI: 10.1021/JA105096R
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摘要: The regioselectivity in the addition of silylboronic esters to terminal alkynes can be switched by choice phosphorus ligands on palladium catalysts. silaboration proceeds with normal regisoselectivity presence (η3-C3H5)Pd(PPh3)Cl (1.0 mol %) give 1-boryl-2-silyl-1-alkenes high yields. In sharp contrast, selective formation inverse regioisomers, 2-boryl-1-silyl-1-alkenes, takes place when reaction is carried out a catalyst bearing P(t-Bu)2(biphenyl-2-yl). A mechanism for change that involves reversible insertion/β-boryl elimination steps proposed.
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