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Synlett 2024; 35(03): 342-346
DOI: 10.1055/a-2131-3368
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Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations

Iron-Catalyzed Oxidative Decarboxylation of Oxamic Acids: A Safe and Efficient Photochemical Route to Urethanes

Gülbin Kurtay
a   University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France
b   Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe, 06800, Çankaya, Ankara, Turkey
,
Jonathan Lusseau
a   University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France
,
Frédéric Robert
a   University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France
,
Yannick Landais  ∗
a   University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France
› Author AffiliationsG.K. thanks the TUBITAK BIDEB-2219 program for a postdoctoral grant (1059B191900553). The Agence Nationale de la Recherche (ANR) (NCO-INNOV, No. 20-CE07-0015-01), the University of Bordeaux (UB), and the CNRS are gratefully acknowledged for their financial support.
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Abstract

This study presents a facile method for synthesizing urethanes through the photocatalyzed oxidative decarboxylation of oxamic acids. The process involves the formation of an isocyanate in situ from an oxamic acid under blue-light irradiation (427 nm) in the presence of ferrocene as a photocatalyst, 2-picolinic acid as a ligand, and potassium bromate as an oxidant. The one-pot procedure effectively avoids the need for separation, purification, and storage of carcinogenic isocyanates, making it a safer and more practical method for obtaining target urethanes from easily accessible starting materials.

Key words

urethanes - oxamic acids - iron catalysis - ferrocene - photocatalysis - decarboxylation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2131-3368.
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Publication History

Received: 23 May 2023

Accepted after revision: 17 July 2023

Accepted Manuscript online:
17 July 2023

Article published online:
07 September 2023

© 2023. Thieme. All rights reserved

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  • 22 Carbamates 2a–v; General Procedure A 10 mL vial equipped with a Teflon septum and a magnetic stirrer bar was charged with the appropriate oxamic acid 1 (1.0 equiv, 0.5 mmol), ferrocene (2.5 mol%, 0.0125 mmol), 2-picolinic acid (5.0 mol%, 0.0250 mmol), and KBrO3 (2 equiv, 1.0 mmol). The vial was then degassed with N2 for about 10 min using an outlet needle before distilled dried DCE (5 mL) and the appropriate alcohol ROH (2.0 equiv, 1.0 mmol) were added. The purge process was repeated by sparging with N2 for 5 min, and then the reaction vial was irradiated with a Kessil lamp (40 W, 427 nm LEDs) at a distance of 5 cm for 24 h. When the reaction was complete, the crude product was collected by evaporation of the mixture and purified by flash chromatography (silica gel, usually EtOAc–hexane). Ethyl (4-Methylbenzyl)carbamate (2a) White solid; yield: 85 mg (87%); mp 55–57 °C (EtOAc–hexane, 10:90); Rf = 0.28 (EtOAc–hexane, 10:90). FTIR (KBr): 3352, 2924, 1948, 1708, 1451, 1248, 1132, 1036, 797, 469 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.15 (t, J = 6.9 Hz, 4 H), 4.94 (s, 1 H), 4.32 (d, J = 5.9 Hz, 2 H), 4.14 (q, J = 7.1 Hz, 2 H), 2.33 (s, 3 H), 1.25 (t, J = 7.1 Hz, 3 H). 13C NMR (76 MHz, CDCl3): δ = 156.8, 137.2, 135.7, 129.4, 127.6, 61.0, 44.9, 21.2, 14.8. HRMS (ESI): m/z [M + Na]+ calcd for C11H15NNaO2: 216.09950; found: 216.09890.