New Results on the Triplet Photoreactivity of β,γ-Unsaturated Aldehydes: Diastereoselective Synthesis of Cyclopropanecarbaldehydes

Diego Armesto; Maria J. Ortiz; Antonia R. Agarrabeitia; Santiago Aparicio-Lara

doi:10.1055/s-2001-15059

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Synthesis 2001(8): 1149-1158
DOI: 10.1055/s-2001-15059

PAPER

New Results on the Triplet Photoreactivity of β,γ-Unsaturated Aldehydes: Diastereoselective Synthesis of Cyclopropanecarbaldehydes

Diego Armesto*, Maria J. Ortiz*, Antonia R. Agarrabeitia, Santiago Aparicio-Lara
Departamento de Quimica Organica I, Facultad de Ciencias Quimicas, Universidad Complutense, 28040-Madrid, Spain
Fax: +34(91)3944103; e-Mail: darmesto@eucmos.sim.ucm.es;

Further Information

Publication History

Received 1 February 2001
Publication Date:
24 September 2004 (online)

Abstract
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Abstract

A comparative study on the triplet photoreactivity of a series of β,γ-unsaturated aldehydes and methyl ketones has been carried out. Aldehydes 14 and 20 were found to undergo the oxa-di-p-methane rearrangement yielding the corresponding cyclopropane carbaldehydes 15 and 21 diastereoselectively. Decarbonylations and 1,3-carbonyl migrations have been observed in some cases, although these reactions do not take place via a Norrish Type I mechanism.

Keywords

β,γ-unsaturated carbonyl compounds - oxa-di-p-methane rearrangement - decarbonylation - cyclopropanecarbaldehydes - 1,3-formyl migration.

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Aldehydes 15a-b and 21a-d undergo spontaneous oxidation in the presence of atmospheric oxygen. The combustion analyses quoted correspond to the carboxylic acids resulting from oxidation.