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. 2025 Feb 1:171:134418.
doi: 10.1016/j.tet.2024.134418. Epub 2024 Dec 9.

TBAT-Catalyzed Dioxasilinane Formation from Beta-Hydroxy Ketones

H J Peterson  1 , G W O'Neil  1
Affiliations

TBAT-Catalyzed Dioxasilinane Formation from Beta-Hydroxy Ketones

H J Peterson et al. Tetrahedron. .

Abstract

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 dioxasilinane 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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Conflict of interest statement

Declaration of interests The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Gregory O’Neil reports financial support was provided by National Institutes of Health. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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