ビニルシランと白金触媒を用いる新規有機合成反応の開発《マイレビュー》

Abstract

Vinylsilanes have frequently been used as carbon nucleophiles for efficient, stereospecific carbon-carbon bond formation. Their reactions occur usually at the position a to silicon. We herein report the Pt(II)-catalyzed nucleophilic addition of vinylsilanes at the b- or g-position leading to vinylation or allylation products, respectively. Under catalysis by PtCl2-2LiI, (Z)-vinylsilanes reacted with aromatic aldehydes at the position b to silicon, affording allyl silyl ethers in good to high yields. Use of MnI2 instead of LiI was effective in the vinylation of aliphatic aldehydes. We also succeeded in the one-pot vinylation of aldehydes with terminal alkynes and Et3SiH, in which PtCl2 successively catalyzed hydrosilylation of alkynes with Et3SiH and vinylation of aldehydes with the vinylsilanes formed. In contrast, under catalysis by PtCl2-2AgSbF6, the reaction of (Z)-vinylsilanes with dimethyl acetals proceeded at the g-position to give homoallylic ethers in good to high yields. When aldehydes and HC(OMe)3 were used instead of dimethyl acetals, the allylation products were obtained directly from aldehydes.textapplication/pdfdepartmental bulletin pape