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

Chaorong Qi; Tianzuo Guo; Wenfang Xiong

doi:10.1055/s-0035-1560561

Synlett, Table of Contents

Synlett 2016; 27(18): 2626-2630
DOI: 10.1055/s-0035-1560561

letter

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

Authors

Chaorong Qi*

School of Chemistry and Chemical Engineering, State Key Lab of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: crqi@scut.edu.cn
Tianzuo Guo

School of Chemistry and Chemical Engineering, State Key Lab of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: crqi@scut.edu.cn
Wenfang Xiong

School of Chemistry and Chemical Engineering, State Key Lab of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: crqi@scut.edu.cn

Abstract

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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

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References

References and Notes

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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.
17 Analytical Data of Two New Compounds 4-Isopropylphenyl Diethylcarbamodithioate (3ca) Colorless solid (123.5 mg, 98%); mp 80–81 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.39 (d, J = 8.0 Hz, 2 H), 7.28 (d, J = 8.0 Hz, 2 H), 4.01 (q, J = 8.0 Hz, 2 H), 3.83 (q, J = 8.0 Hz, 2 H), 2.99–2.90 (m, 1 H), 1.36 (t, J = 6.0 Hz, 3 H), 1.27 (d, J = 4.0 Hz, 9 H).¹³C NMR (100 MHz, CDCl₃): δ = 196.02, 150.51, 136.73, 128.18, 126.99, 49.57, 46.97, 33.66, 23.54, 12.53, 11.37. IR (KBr): 2962, 2870, 1592, 1486, 1414, 1265, 1205, 1142, 1101, 976, 827, 548 cm^–1. MS (EI): m/z = 267[M⁺], 135, 116 (100), 91, 88. ESI-HRMS: m/z calcd for C₁₄H₂₁NS₂Na [M + Na]⁺: 290.1008; found: 290.1014.Phenyl Dipropylcarbamodithioate (3ac) Yellow oil (98.7 mg, 78%). ¹H NMR (400 MHz, CDCl₃): δ = 7.48–7.39 (m, 5 H), 3.90 (t, J = 6.0 Hz, 2 H), 3.72 (t, J = 8.0 Hz, 2 H), 1.88–1.74 (m, 4 H), 1.01 (t, J = 6.0 Hz, 3 H), 0.92 (t, J = 6.0 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 196.27, 136.93, 131.57, 129.69, 128.81, 56.92, 54.71, 20.81, 19.47, 11.09. IR (KBr): 2968, 2871, 1482, 1410, 1238, 1194, 1145, 986, 745, 686, 503 cm^–1. MS (EI): m/z = 253 [M⁺], 153, 144 (100), 109, 102, 77, 60. ESI-HRMS: m/z calcd for C₁₃H₁₉NS₂Na [M + Na]⁺: 276.0851; found: 276.0853.

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Supplementary Material

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