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Acta Chimica Sinica >

2020 , Vol. 78 >Issue 10: 1064 - 1068

DOI: https://doi.org/10.6023/A20070296

Communication

A New Strategy for the Synthesis of Tertiary Amides via a Copper-Catalyzed Decyanation Reaction of N,N-Disubstituted 2-Aminomalononitriles

  • Liang Huan ,
  • Gou Along ,
  • Gao Zhupeng ,
  • Lei Linsheng ,
  • Wang Bowen ,
  • Yu Lan ,
  • Xu Xuetao ,
  • Wang Shaohua
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  • a School of Pharmacy, Lanzhou University, Lanzhou 730000, China;
    b School of Biotechnology and Health Sciences, Wuyi University, Jiangmen 529020, China

Received date: 2020-07-07

  Online published: 2020-09-09

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21472077, 21772071) and Department of Education of Guangdong Province (Nos. 2017KTSCX185, 2017KSYS010, 2016KCXTD005, 2019KZDXM035). Chinese patent pending (No. 202010648789.7).

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Abstract

The development of new synthetic methodology and reagent is always a hot topic in organic synthesis community. Among the strategies used, chemical property investigation of synthetic intermediates with multifunctional groups represents a direct and efficient way. In this paper, as a systematic continuation of α-aminomalononitrile based synthetic application studies, α-aminomalononitrile has been developed for the first time as a surrogate for carbamoyl anions and applied to the synthesis of tertiary amides via a copper-catalyzed decyanation reaction. This strategy features simple reaction conditions, scalability, and wide substrate scope. This work not only further enriches the reaction model of aminonitrile compounds, but also provides an alternative synthetic strategy for the synthesis of substituted amides from simple formamides. In this process, the substrates could be readily synthesized through the nucleophilic addition or substitution reaction of α-aminomalononitriles, and they would be converted to corresponding tertiary amide in the presence of CuF2 in DMSO. As an example, the formal hydrocarbamoylation reaction of unsaturated bonds could be achieved. A general procedure for the strategy is as follows:α-aminomalononitrile derived from formamide is used to undergo nucleophilic addition or substitution reaction with electrophilic reagents. Next, the two cyano groups of the synthesized substrates could be removed under the catalysis of CuF2 to form a C=O double bond in situ, thereby achieving the synthesis of corresponding tertiary amide. During the reaction, the α-aminomalononitrile substrate (0.4 mmol), CuF2 (5 mol%), DMSO (3 mL) were placed in a sealed reaction tube at 100℃ at an argon atmosphere for about 32 hours. Then, the reaction system was washed out with ethyl acetate, and the organic phase was washed with water to remove DMSO. Next, the aqueous phase was extracted with ethyl acetate. Finally all organic phases were combined, washed once with saturated brine. After drying the organic phase over anhydrous sodium sulfate, it was concentrated by a vacuum pump. Finally, the residue was purified by flash column chromatography to give amide product.

Key words： α-aminomalononitriles; formamides; carbamoyl anion; copper catalysis

Cite this article

Liang Huan , Gou Along , Gao Zhupeng , Lei Linsheng , Wang Bowen , Yu Lan , Xu Xuetao , Wang Shaohua . A New Strategy for the Synthesis of Tertiary Amides via a Copper-Catalyzed Decyanation Reaction of N,N-Disubstituted 2-Aminomalononitriles[J]. Acta Chimica Sinica, 2020 , 78(10) : 1064 -1068 . DOI: 10.6023/A20070296

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