Metal-Free Electrochemical Reduction of Disulfides in an Undivided Cell under Mass Transfer Control.

Autor: Malviya BK; Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010, Graz, Austria.; Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, 8010, Graz, Austria., Hansen EC; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Kong CJ; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Imbrogno J; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Verghese J; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Guinness SM; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Salazar CA; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Desrosiers JN; Chemical Research & Development, Pfizer Worldwide Research & Development, Groton, Connecticut, 06340, USA., Kappe CO; Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010, Graz, Austria.; Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, 8010, Graz, Austria., Cantillo D; Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010, Graz, Austria.; Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, 8010, Graz, Austria.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Nov 24; Vol. 29 (66), pp. e202302664. Date of Electronic Publication: 2023 Oct 11.
DOI: 10.1002/chem.202302664
Abstrakt: Electroorganic synthesis is generally considered to be a green alternative to conventional redox reactions. Electrochemical reductions, however, are less advantageous in terms of sustainability, as sacrificial metal anodes are often employed. Divided cell operation avoids contact of the reduction products with the anode and allows for convenient solvent oxidation, enabling metal free greener electrochemical reductions. However, the ion exchange membranes required for divided cell operation on a commercial scale are not amenable to organic solvents, which hinders their applicability. Herein, we demonstrate that electrochemical reduction of oxidatively sensitive compounds can be carried out in an undivided cell without sacrificial metal anodes by controlling the mass transport to a small surface area electrode. The concept is showcased by an electrochemical method for the reductive cleavage of aryl disulfides. Fine tuning of the electrode surface area and current density has enabled the preparation of a wide variety of thiols without formation of any oxidation side products. This strategy is anticipated to encourage further research on greener, metal free electrochemical reductions.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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