tbat催化β -羟基酮生成二恶硅烷。

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron Pub Date : 2025-02-01 DOI:10.1016/j.tet.2024.134418

H.J. Peterson, G.W. O'Neil

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引用次数: 0

摘要

β -羟基酮可以通过钌催化的硅醚化反应，然后是四丁基氟化铵（TBAF）促进的分子内硅氢化反应来还原。从TBAF转换到四丁基二氟三苯硅酸盐铵（TBAT），即使没有首先形成硅基醚，也会产生环二恶硅烷产品。这些比较敏感的化合物可以用florisil作为固定相的柱层析纯化。或者，用甲基锂选择性地打开二恶硅烷的区域，提供相应的分化的1,3-二醇作为其二苯基甲基硅基（DPMS）醚的选择性保护。提出了tbat催化硅醚形成的机理，然后是tbat促进的分子内羰基硅氢化反应。观察到的反应非对映选择性支持了这一机制，这与其他被认为是在分子内进行的羰基硅氢化反应一致。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

TBAT-catalyzed dioxasilinane formation from beta-hydroxy ketones

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TBAT-catalyzed dioxasilinane formation from beta-hydroxy ketones

Beta-hydroxy ketones can be reduced using a sequence of ruthenium-catalyzed silyl etherification followed by tetrabutylammonium fluoride (TBAF) promoted intramolecular hydrosilylation. Switching from TBAF to tetrabutylammonium difluorotriphenylsilicate (TBAT), even without first forming the silyl ether, gave cyclic dioxasilinane products. These somewhat sensitive compounds could be isolated pure by column chromatography using florisil as the stationary phase. Alternatively, the dioxasilinanes were regioselectively opened with methyl lithium, affording the corresponding differentiated 1,3-diol with selective protection of the secondary alcohol as its diphenylmethylsilyl (DPMS) ether. A mechanism is proposed involving TBAT-catalyzed silyl ether formation followed by TBAT-promoted intramolecular carbonyl hydrosilylation. This mechanism is supported by the observed diastereoselectivity of the reaction, which was consistent with other carbonyl hydrosilylations thought to proceed intramolecularly.

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来源期刊

Tetrahedron 化学-有机化学

CiteScore

3.90

自引率

4.80%

发文量

439

审稿时长

34 days

期刊介绍： Tetrahedron publishes full accounts of research having outstanding significance in the broad field of organic chemistry and its related disciplines, such as organic materials and bio-organic chemistry. Regular papers in Tetrahedron are expected to represent detailed accounts of an original study having substantially greater scope and details than that found in a communication, as published in Tetrahedron Letters. Tetrahedron also publishes thematic collections of papers as special issues and ''Reports'', commissioned in-depth reviews providing a comprehensive overview of a research area.