Anodic Oxidation of Dithiane Carboxylic Acids: A Rapid and Mild Way to Access Functionalized Orthoesters

Anthony D. Garcia, Matthew C. Leech, Alessia Petti, Camille Denis, Iain C. A. Goodall, Adrian P. Dobbs and Kevin Lam*

*School of Science, University of Greenwich, Chatham, Kent, Chatham Maritime ME4 4TB, United Kingdom, Email: k.lamgreenwich.ac.uk

A. D. Garcia, M. C. Leech, A. Petti, C. Denis, I. C. A. Goodall, A. P. Dobbs, K. Lam, Org. Lett., 2020, 22, 3875-3878.

DOI: 10.1021/acs.orglett.0c01324

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Abstract

A wide variety of functionalized orthoesters can be prepared under mild and green electrochemical conditions from easily accessible dithiane derivatives.

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Representative Procedure. Synthesis of Orthoester 8a.

A 10 mL IKA Electrasyn electrochemical cell was charged with dithiane 5a (0.09 mmol), methanol (10 mL) and NaOMe solution (0.04 mL, 5.4 M in methanol, 0.22 mmol), and the resulting solution electrolysed (constant current, 100 mA.cm-2, 30 F mol^-1 ). Upon completion, the reaction mixture was poured into a mixture of 10% aqueous NaOH Solution (5 mL) and hexanes (5 mL). The product was then extracted with hexanes (3 x 10 mL), before the extracts were combined and dried over Na₂SO₄. Removal of solvent under reduced pressure afforded the desired orthoester.

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Key Words

ortho esters, 1,3-dithianes, electrochemistry

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ID: J54-Y2020