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Thermolysis of imidates: A new method for the generation of carbonyl ylides


Nikolaev, V V; Linden, A; Heimgartner, H (2007). Thermolysis of imidates: A new method for the generation of carbonyl ylides. Helvetica Chimica Acta, 90(12):2330-2341.

Abstract

Thermolysis of dimethyl 2-[(3-oxo-3H-isoindol-1-yl)oxy]malonate (8) promotes a [1,4]-H shift in the imidic N¼C O CH fragment of the starting molecule, which leads to a reactive carbonyl ylide. This carbonyl ylide can be trapped by the C¼N bond of imidates and imines, as well as the C¼O bond of
benzaldehyde. The corresponding cycloadducts 11, 14, and 16 are formed regioselectively in good yields (60 – 95%) and with high stereoselectivity. In the case of 11, the minor cycloadduct in solution undergoes an isomerization to give the more stable stereoisomer. The structures of two cycloadducts, i.e., 11a and
14a, have been established by X-ray crystallography.

Thermolysis of dimethyl 2-[(3-oxo-3H-isoindol-1-yl)oxy]malonate (8) promotes a [1,4]-H shift in the imidic N¼C O CH fragment of the starting molecule, which leads to a reactive carbonyl ylide. This carbonyl ylide can be trapped by the C¼N bond of imidates and imines, as well as the C¼O bond of
benzaldehyde. The corresponding cycloadducts 11, 14, and 16 are formed regioselectively in good yields (60 – 95%) and with high stereoselectivity. In the case of 11, the minor cycloadduct in solution undergoes an isomerization to give the more stable stereoisomer. The structures of two cycloadducts, i.e., 11a and
14a, have been established by X-ray crystallography.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2007
Deposited On:20 Oct 2011 12:09
Last Modified:05 Apr 2016 15:02
Publisher:Verlag Helvetica Chimica Acta
ISSN:0018-019X
Funders:F. Hoffmann-La Roche AG, Basel
Publisher DOI:10.1002/hlca.200790239
Permanent URL: http://doi.org/10.5167/uzh-50021

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