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Synlett 2017; 28(16): 2139-2142
DOI: 10.1055/s-0036-1589061
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© Georg Thieme Verlag Stuttgart · New York

Potassium tert-Butoxide Mediated Arylation of 2-Substituted Malononitriles Using Diaryliodonium Salts

Jianwei Han*
a   Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: jianweihan@ecust.edu.cn   Email: wanglimin@ecust.edu.cn
b   Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200237, P. R. of China
,
Xiaofei Qian
a   Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: jianweihan@ecust.edu.cn   Email: wanglimin@ecust.edu.cn
,
Bowen Xu
a   Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: jianweihan@ecust.edu.cn   Email: wanglimin@ecust.edu.cn
,
Limin Wang*
a   Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: jianweihan@ecust.edu.cn   Email: wanglimin@ecust.edu.cn
› Author AffiliationsThe work was supported by the National Nature Science Foundation of China (NSFC 21472213, 21272069), National Key Program (2016YFA0200302, Study on application and preparation of aroma nanocomposites), and the Fundamental Research Funds for the Central Universities.
Further Information

Publication History

Received: 24 April 2017

Accepted after revision: 22 May 2017

Publication Date:
06 July 2017 (online)

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Abstract

Direct arylation of 2-substituted malononitriles using diaryliodonium salts without involving transition-metal catalysts was developed. By using potassium tert-butoxide as a promoter, the desired 2-substituated α-arylmalononitriles derivatives were synthesized in good to excellent yields of 55–96%. This synthetic method provided an efficient way to prepare a variety of 2-substituted arylmalononitriles which were useful in agrochemicals.

Key words

arylation - diaryliodonium salts - metal-free - arylmalononitriles - agrochemicals

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589061.
  • Supporting Information
 

  • References and Notes

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  • 11 General Procedure for the Synthesis of 3 and 4 An oven-dried Schlenk tube was charged with 2-substituted malononitriles (0.5 mmol, 1 equiv), the tube was evacuated and charged with nitrogen, then 2 mL anhydrous DCM and t-BuOK (61.7 mg, 0.55 mmol, 1.1 equiv) were added, and the mixture was stirred at 0 °C for 5 min. The solution of diaryliodonium salts (0.55 mmol, 1.1 equiv) in 2 mL anhydrous DCM was added through a syringe subsequently for 5 min. The reaction was stirred for another 1 h, and the reaction temperature was elevated to r.t. The reaction mixture was quenched with 20 mL water, then the mixture was extracted with EtOAc (3 × 10 mL). The combined extracts were washed with brine, dried over Na2SO4, and filtered. After the solvent was removed under vacuum, and the residue was purified by flash chromatography to give the desired product. Analytical data for representative sample 3a is provided below. 2-Ethyl-2-phenylmalononitrile (3a) 81.7 mg (96% yield), colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.58–7.53 (m, 2 H), 7.52–7.45 (m, 3 H), 2.29 (q, J = 7.4 Hz, 2 H), 1.23 (t, J = 7.4 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 132.0, 129.9, 129.7, 125.8, 115.0, 43.2, 36.6, 10.0. HRMS (EI): m/z calcd for C11H10N2 [M]+: 170.0844; found: 170.0843.