有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
ケイ素-炭素結合の酸化的切断反応
ポリオール合成における新手法
玉尾 皓平
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ジャーナル フリー

1988 年 46 巻 9 号 p. 861-878

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Origin and application of oxidative cleavages of the silicon-carbon bonds have been reviewed.While siliconcarbon bonds have been well known to be extremely stable to oxidizing agents or aerobic oxidation, we have recently found facile oxidative cleavages of the silicon-carbon bonds in certain silafunctional compounds by hydrogen peroxide, peracid, and dioxygen.The presence of at least one functional group (hetero atom) on silicon is essential for the oxidation.Fluoride ions promote the oxidation.
The article includes the following topics. (1) An important role of penta- and hexa-coordinate species for the activation of the silicon-carbon bond toward oxidizing agents. (2) Characteristic features, stereochemistry, and general scope- and-limitations of the hydrogen peroxide oxidation. (3) Applications of the hydrogen peroxide oxidation to regio- and stereo-selective synthesis of polyhydroxylated molecules by the use of multi-functional silicon reagents.Hydrosilanes, silyl anions, silylmethyl Grignard reagents, silylmethyl bromide, 1-bromovinylsilanes, and allylsilanes have been used to be synthons of HO (+) , HO (-) , HOCH2 (-) , HOCH2 (·) , MeCO (·) , α-hydroxyallyl anion etc. (4) Oxidation by dioxygen under a biomimetic flavin-based redox condition.

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