Iridium-Catalyzed Regioselective Silylation of Secondary Alkyl C鈥揌 Bonds for the Synthesis of 1,3-Diols

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• 作者：Bijie Li ; Matthias Driess ; John F. Hartwig
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：May 7, 2014
• 年：2014
• 卷：136
• 期：18
• 页码：6586-6589
• 全文大小：318K
• 年卷期：v.136,no.18(May 7, 2014)
• ISSN：1520-5126

文摘

We report Ir-catalyzed intramolecular silylation of secondary alkyl C鈥揌 bonds. (Hydrido)silyl ethers, generated in situ by dehydrogenative coupling of a tertiary or conformationally restricted secondary alcohol with diethylsilane, undergo regioselective silylation at a secondary C鈥揌 bond 纬 to the hydroxyl group. Oxidation of the resulting oxasilolanes in the same vessel generates 1,3-diols. This method provides a strategy to synthesize 1,3-diols through a hydroxyl-directed, functionalization of secondary alkyl C鈥揌 bonds. Mechanistic studies suggest that the C鈥揌 bond cleavage is the turnover-limiting step of the catalytic cycle. This silylation of secondary C鈥揌 bonds is only 40鈥?0 times slower than the analogous silylation of primary C鈥揌 bonds.