Efficient Synthesis of Carboxylic Esters via Palladium(II)-Catalyzed Direct Alkoxycarbonylation of Arenes with CO and Alcohols

Abstract

An efficient palladium(II)-catalyzed procedure for the alkoxycarbonylation of arenes and heteroarenes with atmospheric pressure carbon monoxide and alcohols was developed to synthesize aryl carboxylic esters.

Key words

palladium - C–H activation - alkoxycarbonylation - CO - carboxylic esters

• References and Notes


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• 11 General Procedure for Alkoxycarbonylation of 1 with CO and Alcohols A mixture of substrate 1 (0.2 mmol), Pd(OAc)₂ (10 mmol%), CuBr₂ (0.2 mmol), NaOAc (0.3 mmol), alcohol (3.0 mmol), and dioxane (2.0 mL) in a 50 mL Schlenk tube (purged with CO/O₂ = 4:1) was heated at 100 °C for 24 h. The reaction mixture was cooled to r.t. and concentrated in vacuo. The residue was purified by chromatography on silica gel to afford the desired product 2. Pentyl 4-Methyl-2-(pyridin-2-yl)benzoate (2b) Compound 2b was prepared in 63% yield according to the general procedure as an oil. ¹H NMR (400 MHz, CDCl₃): δ = 8.64 (d, J = 4.8 Hz, 1 H), 7.77 (d, J = 7.6 Hz, 1 H), 7.72 (d, J = 7.6 Hz, 1 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.34 (s, 1 H), 7.27 (d, J = 7.6 Hz, 2 H), 4.04 (t, J = 6.8 Hz, 2 H), 2.43 (s, 3 H), 1.41–1.35 (m, 2 H), 1.25–1.19 (m, 2 H), 1.11–1.04 (m, 2 H), 0.83 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.6, 159.2, 149.0, 141.6, 141.2, 135.9, 130.7, 130.1, 128.9, 123.0, 121.9, 55.0, 28.0, 22.3, 21.4, 13.9. HRMS (EI-TOF): m/z calcd for C₁₈H₂₁NO₂ [M⁺]: 283.1572; found: 283.1573.
• 12 Macgregor SA, Neave GW. Organometallics 2003; 22: 4547
• 13 While this manuscript was under revision, a Pd-catalyzed direct C–H activation–carbonylation of 2-arylphenols was reported: Luo S, Luo F.-X, Zhang X.-S, Shi Z.-J. Angew. Chem. Int. Ed. 2013; 52: 10598