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Molecules 2011, 16(6), 5062-5078; doi:10.3390/molecules16065062
Article

Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes

1, 2 and 1,*
1 Unit of Crop Bioprotection Research, USDA, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University Street, Peoria, IL 61604, USA 2 Unit of Functional Food Research, USDA, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University Street, Peoria, IL 61604, USA
* Author to whom correspondence should be addressed.
Received: 28 April 2011 / Revised: 31 May 2011 / Accepted: 13 June 2011 / Published: 17 June 2011
(This article belongs to the Special Issue Protecting Group in Organic Synthesis)
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Abstract

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps.
Keywords: aldehyde homologation; ketone to aldehyde homologation; diethyl methylformyl-phosphonate dimethylhydrazone; diethyl ethylformyl-2-phosphonate dimethylhydrazone aldehyde homologation; ketone to aldehyde homologation; diethyl methylformyl-phosphonate dimethylhydrazone; diethyl ethylformyl-2-phosphonate dimethylhydrazone
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).
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Petroski, R.J.; Vermillion, K.; Cossé, A.A. Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes. Molecules 2011, 16, 5062-5078.

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