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.
Highlights
This article has been edited by the Royal Society of Chemistry, including the commissioning, peer review process and editorial aspects up to the point of acceptance
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-2,5dihydrofuran
Little attention seems to have been paid to this electrochemical route in recent years, aside from a report by Horii et al [16] describing the electrosynthesis of 2,5-diacetoxy-2,5dihydrofuran in a thin-layer flow cell
Summary
This article has been edited by the Royal Society of Chemistry, including the commissioning, peer review process and editorial aspects up to the point of acceptance. An attractive route for obtaining such products without the use of toxic lead salts is the electrochemical oxidation of furan in the presence of acetate to give 2,5-diacetoxy-2,5-dihydrofuran This approach was first reported by Wilson & Lippincott [14], and subsequently developed firstly by Baggaley & Brettle [15] and by Shono et al [7]. Little attention seems to have been paid to this electrochemical route in recent years, aside from a report by Horii et al [16] describing the electrosynthesis of 2,5-diacetoxy-2,5dihydrofuran in a thin-layer flow cell This last work is the only report of the electrochemical synthesis of a 2,5-dicarboxy-2,5-dihydrofuran with a comprehensive and detailed experimental procedure. All these electrosynthesis methods have been conducted under constant current conditions
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