Towards a better understanding of the electrosynthesis of 2,5-dicarboxy-2,5-dihydrofurans: structure, mechanism and influence over stereochemistry

Shipman, M. A., Sproules, S. , Wilson, C. and Symes, M. D. (2019) Towards a better understanding of the electrosynthesis of 2,5-dicarboxy-2,5-dihydrofurans: structure, mechanism and influence over stereochemistry. Royal Society Open Science, 6(7), 190336. (doi: 10.1098/rsos.190336) (PMID:31417736) (PMCID:PMC6689595)

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Abstract

2,5-Dicarboxy-2,5-dihydrofurans are key constituents of a number of natural products and have roles as intermediates in the formation of other such compounds of interest. Typically, these species are synthesized using toxic Pb(IV) salts. Electrochemical syntheses of 2,5-diacetoxy-2,5-dihydrofuran that do not require the use of lead have been reported, but a general lack of experimental detail has prevented these procedures from being more widely adopted. Moreover, no electrochemical study has yet reported the ratio of cis and trans isomers produced. Herein, we compare the chemical, lead-based route to 2,5-diacetoxy-2,5-dihydrofuran with a fully described electrosynthesis method. In doing so, we have discovered that the cis and trans isomers of this compound were previously incorrectly assigned in the literature, an error that we correct by obtaining the crystal structure of cis-2,5-diacetoxy-2,5-dihydrofuran. This allows the ratios of the isomers as prepared by the chemical (2 : 1 cis : trans) and electrochemical (7 : 5 cis : trans) methods to be obtained. Through experimental and computational insights, we propose a mechanism for the electrochemical synthesis of 2,5-dicarboxy-2,5-dihydrofurans and go some way towards validating this mechanism by synthesizing 2,5-dibutoxy-2,5-dihydrofuran electrochemically for the first time. We hope that these findings will provide some greater clarity to the literature surrounding the electrosynthesis and potential applications of 2,5-dicarboxy-2,5-dihydrofurans.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen and Wilson, Dr Claire and Symes, Dr Mark and Shipman, Mr Michael
Authors: Shipman, M. A., Sproules, S., Wilson, C., and Symes, M. D.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Royal Society Open Science
Publisher:The Royal Society
ISSN:2054-5703
ISSN (Online):2054-5703
Published Online:10 July 2019
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Royal Society Open Science 6(7):190336
Publisher Policy:Reproduced under a Creative Commons License
Data DOI:10.5525/gla.researchdata.745

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
714601Driving energetically uphill processes using metal-ligand coordination complexesMark SymesThe Royal Society (ROYSOC)UF150104CHEM - CHEMISTRY