Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes 英文参考文献.docVIP

Molecules 2011, 16, 5062-5078; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Articles Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes Richard J. Petroski 1, Karl Vermillion 2 and Allard A. Cossé 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; E-Mail: Allard.Cosse@; Tel.: +1-309-681-6217; Fax: +1-309-681-6693. Received: 28 April 2011; in revised form: 31 May 2011 / Accepted: 13 June 2011 / Published: 17 June 2011 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 1. Introduction A recurring theme in the synthesis of various polyketide natural products and other compounds is two-carbon homologation of ald