Copper-Mediated Coupling of Boronic Acids, Amines, and Carbon Disulfide: An Approach to Organic Dithiocarbamates

Abstract

An efficient copper-mediated three-component coupling reaction of boronic acids, amines, and carbon disulfide has been developed, which provides a new approach to a wide range of functionalized dithiocarbamates in good to excellent yields. The present methodology has many advantages, such as mild reaction conditions, easily available substrates, wide substrate scope, and high functional-group tolerance.

Key words

amine - boron - copper - coupling - multicomponent reaction

• References and Notes

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Representative reviews on Chan–Evans–Lam coupling reaction, see:
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• 16 Typical Procedure for the Synthesis of Compound 3aa A 25 mL dried Schlenk tube was charged with boronic acid 1a (0.5 mmol), diethylamine (2a, 2.5 mmol), CS₂ (1.0 mmol), Cu(OAc)₂ (1.0 mmol), K₂CO₃ (1.5 mmol), and MeCN (4 mL) at room temperature. The reaction mixture was stirred at 60 °C for 10 h under air. After the reaction was completed, the mixture was cooled to room temperature and filtered through a plug of Celite. The filtrate was then concentrated in vacuo to afford the crude product, which was then subjected to chromatography on silica gel with hexanes–EtOAc (20:1) to give the desired product 3aa as a pale yellow oil; 88% isolated yield (96% GC yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.48 (q, J = 8.0 Hz, 5 H), 4.04 (q, J = 4.0 Hz, 2 H), 3.86 (q, J = 8.0 Hz, 2 H), 1.40 (t, J = 8.0 Hz, 3 H), 1.30 (t, J = 8.0 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 195.78, 137.00, 131.47, 129.79, 128.87, 49.71, 47.14, 12.61, 11.46. IR (KBr): 3055, 2978, 2932, 1485, 1444, 1414, 1067, 1009, 978, 915, 826, 744, 685, 505 cm^–1. MS (EI): m/z = 225[M⁺], 152, 141, 116 (100), 109, 88. ESI-HRMS: m/z calcd for C₁₁H₁₅NS₂Na [M + Na]⁺: 248.0538; found: 248.0543.
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