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Synlett 2017; 28(01): 98-102
DOI: 10.1055/s-0036-1588649
DOI: 10.1055/s-0036-1588649
cluster
The Abiotic Oxidation of Organic Acids to Malonate
Further Information
Publication History
Received: 16 August 2016
Accepted after revision: 19 October 2016
Publication Date:
07 November 2016 (online)
Abstract
The nucleophilicity of the α-carbon of malonate, coupled with its potential for subsequent decarboxylation, makes it an intriguing building block in prebiotic chemical scenarios. In this work, a variety of citric acid cycle (TCA) intermediates is shown to unexpectedly generate malonate in an oxidizing environment. The reactions are facile in aqueous solution containing hydrogen peroxide, a prevalent abiotic oxidant. In modern metabolism, malonate is a carbon source for acetyl-CoA. Additionally, its thioester is the substrate for the biosynthesis of both fatty acids and polyketides. The data presented herein may hint at how an early link was formed between polyketide, fatty acid, and TCA pathways.
Key words
malonate - oxidation - bioorganic chemistry - prebiotic chemistry - hydrogen peroxide - carboxylic acids - α-keto acidsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588649.
- Supporting Information
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