Synlett 2017; 28(01): 98-102
DOI: 10.1055/s-0036-1588649
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© Georg Thieme Verlag Stuttgart · New York

The Abiotic Oxidation of Organic Acids to Malonate

Gavin B. Ricea, Jayasudhan R. Yerabolub, Ramanarayanan Krishnamurthyb, Greg Springsteen*a
  • aFurman University, 3300 Poinsett Hwy, Greenville SC 29613, USA   Email: greg.springsteen@furman.edu
  • bThe Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
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Publication History

Received: 16 August 2016

Accepted after revision: 19 October 2016

Publication Date:
07 November 2016 (eFirst)

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.

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