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Silene equivalents through the rhodium-catalysed reactions of alpha-hypersilyl diazoesters: a computational and experimental study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
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2011 (English)In: Chemical Science, ISSN 2041-6520, Vol. 2, no 12, 2367-2372 p.Article in journal (Refereed) Published
Abstract [en]

The generation of silenes through the rhodium-catalysed decomposition of alpha-hypersilyl diazocarbonyl compounds has been explored both computationally and experimentally. This transformation proceeds via a pathway involving initial formation of the carbene, followed by rearrangement, initially to a silene and ultimately to a ketene. Density functional theory (DFT) calculations of model compounds suggested that silene formation was most preferential with electron donating substituents attached to the carbonyl group. The predictions were experimentally evaluated and hypersilyl diazoacetates provided an unusually long-lived species (t(1/2) > 40 h) that reacts as a formal silene equivalent. Further DFT calculations support the formation of an internally stabilised silene in the form of a 1,2-silaoxetene. Importantly the acylsilene-silaoxetene reaction is reversible and consequently this silene equivalent reacts with alpha,beta-unsaturated carbonyl compounds to form cyclic silyl enol ethers which have considerable potential for further synthetic transformations.

Place, publisher, year, edition, pages
2011. Vol. 2, no 12, 2367-2372 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-163253DOI: 10.1039/c1sc00405kISI: 000296745500012OAI: oai:DiVA.org:uu-163253DiVA: diva2:464430
Available from: 2011-12-13 Created: 2011-12-09 Last updated: 2011-12-13Bibliographically approved

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Ottosson, Henrik
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Department of Biochemistry and Organic Chemistry
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