TBAT-catalyzed dioxasilinane formation from beta-hydroxy ketones

被引：0

作者：

Peterson, H. J. ^{[1
]}

O'Neil, G. W. ^{[1
]}

机构：

[1] Western Washington Univ, Dept Chem, Bellingham, WA 98225 USA

来源：

TETRAHEDRON | 2025年 / 171卷

基金：

美国国家卫生研究院;

关键词：

RING STRAIN; (-)-DICTYOSTATIN; SILYLATION; CHEMISTRY; EFFICIENT; ALCOHOLS; ETHER;

D O I：

10.1016/j.tet.2024.134418

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页数：7