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Synlett 2016; 27(18): 2626-2630
DOI: 10.1055/s-0035-1560561
letter
© Georg Thieme Verlag Stuttgart · New York

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

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
› Author Affiliations
Further Information

Publication History

Received: 25 May 2016

Accepted after revision: 17 July 2016

Publication Date:
08 August 2016 (online)

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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

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560561.
  • Supporting Information
 

  • 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.
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