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

Gülbin Kurtay; Jonathan Lusseau; Frédéric Robert; Yannick Landais

doi:10.1055/a-2131-3368

Synlett, Table of Contents

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

^aUniversity of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France

^bDepartment of Chemistry, Faculty of Science, Hacettepe University, Beytepe, 06800, Çankaya, Ankara, Turkey

,

Jonathan Lusseau

^aUniversity of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France

,

Frédéric Robert

^aUniversity of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France

,

Yannick Landais ∗

^aUniversity of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France

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Abstract

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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

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References

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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); R_f = 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.

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