Decarboxylative Oxidation of Carboxylic Acids Using Photocatalysis and Copper Catalysis

Abstract

A decarboxylative oxidation of carboxylic acids was developed through visible-light-induced photocatalysis with molecular oxygen as a green oxidant and copper as a co-catalyst. This reaction worked smoothly on various type of acids, and could potentially be used in modifications of natural products. The high efficiency of this transformation was demonstrated on over 40 substrates.

Publication History

Received: 25 April 2023

Accepted after revision: 30 May 2023

Accepted Manuscript online:
30 May 2023

Article published online:
20 July 2023

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• 12 Photocatalytic Decarboxylation: General Procedure A 25 mL round-bottom flask equipped with a stirrer bar was charged with the appropriate substrate 1 (0.5 mmol, 1.0 equiv), [Ir(dF(CF₃)ppy)₂(dtbpy)]PF₆ (16.9 mg, 3 mol%), CuO (7.9 mg, 20 mol%), bathophenanthroline (41 mg, 25mol%), and Cs₂CO₃(243 mg, 1.5 equiv). DCM (10 mL) was added, then the flask was quickly degassed three times and flushed with O₂ from a balloon. The mixture was heated to 40 °C and irradiated with six 100 W blue LEDs (5 cm away) for 40 h. When the reaction was complete, the solvent was removed under a vacuum and the mixture was purified by flash chromatography (silica gel, PE–EtOAc). Benzyl 4-Oxopiperidine-1-carboxylate (2a) Prepared by the general procedure as a yellow liquid; yield: 99 mg (85%). IR (KBr): 2359, 1699, 1630, 1429, 1353 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.36–7.28 (m, 5 H), 5.15 (s, 2 H), 3.76 (t, J = 6.3 Hz, 4 H), 2.42 (t, J = 5.9 Hz, 4 H). ¹³C NMR (101 MHz, CDCl₃): δ = 207.09, 155.05, 136.32, 128.54, 128.20, 127.99, 67.55, 43.07, 40.99. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₃H₁₅NNaO₃: 256.0944; found: 256.0910. The spectra matched those reported in Ref. 10. 4-Fluorobenzaldehyde (2b) Prepared by the general procedure as a yellow liquid; yield: 45.5 mg (73%). IR (KBr): 1652, 1632, 1585, 1373, 1350 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 9.96 (s, 1 H), 7.96–7.85 (m, 2 H), 7.21 (t, J = 8.5 Hz, 2 H). MS (ESI): m/z = 147.1 [M + Na]⁺. The spectra matched those reported in Ref. 11.