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,* email
Received: 28 April 2011; in revised form: 31 May 2011 / Accepted: 13 June 2011 / Published: 17 June 2011
(This article belongs to the Special Issue Protecting Group in Organic Synthesis)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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
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MDPI and ACS Style

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.

AMA Style

Petroski RJ, Vermillion K, Cossé AA. Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes. Molecules. 2011; 16(6):5062-5078.

Chicago/Turabian Style

Petroski, Richard J.; Vermillion, Karl; Cossé, Allard A. 2011. "Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes." Molecules 16, no. 6: 5062-5078.

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