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Synlett 2020; 31(07): 713-717
DOI: 10.1055/s-0039-1691590
DOI: 10.1055/s-0039-1691590
letter
Difluorocarbene-Based Cyanation of Aryl Iodides
The authors thank the National Natural Science Foundation (21421002, 21672242, 21971252), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (CAS) (QYZDJSSW-SLH049), the Youth Innovation Promotion Association CAS (2019256), the Fujian Institute of Innovation, CAS (FJCXY18040102), the Shanghai Research Institute of Chemical Industry Co., Ltd. (SKL-LCTP-201802), the Hunan Provincial Hengyang City Joint Fund Project (2018JJ4036), the general project of the University of South China (18C0438), the Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study (0223-0007-000004), and the Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, CAS (2018-10) for financial support.Weitere Informationen
Publikationsverlauf
Received: 15. Januar 2020
Accepted after revision: 15. Januar 2020
Publikationsdatum:
03. Februar 2020 (online)
◊ These authors contributed equally to this work.
Abstract
A large number of efficient cyanation methods have been developed because of the wide range of applications of nitriles, but conventional methods usually suffer from the need for a toxic cyanation reagent. Although difluorocarbene chemistry has received increasing attention, the use of difluorocarbene as a sources of the nitrile carbon for nitrile groups remains largely unexplored. We describe a difluorocarbene-based cyanation of aryl iodides promoted by a cheap copper source, Cu(NO3)2·2.5H2O, under an air atmosphere. Ph3P+CF2CO2 –, an easily available and shelf-stable difluorocarbene reagent, and NaNH2 are used as the carbon source and the nitrogen source for the nitrile group, respectively. The cyanation protocol is attractive because no toxic reagent is used and performing the reactions under an air atmosphere is operationally convenient.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1691590.
- Supporting Information
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- 31 Cyanation of Aryl Iodides 1; General Procedure Under air atmosphere, a reaction tube was charged with the appropriate aryl iodide 1 (0.5 mmol), Ph3P+CF2CO2 – (268 mg, 0.75 mmol, 1.5 equiv), ligand L4 (6.3 mg, 5 mol%), Cu(NO3)2·2.5 H2O (143 mg, 0.65 mmol, 1.3 equiv), NaNH2 (39 mg, 1.0 mmol, 2.0 equiv), and anhyd DMF (4 mL). The mixture was stirred at 130 °C for 15 h, then cooled to rt and filtered through a pad of Celite that was washed with CH2Cl2. The combined organic phase was washed with H2O (3 × 15 mL), and the organic layer was further washed with sat. aq Na2SO3 and sat. brine, then dried (Na2SO4) and concentrated under vacuum. The residue was purified by flash column chromatography. 9,9-Dimethyl-9H-fluorene-3-carbonitrile (2k) The reaction was performed on a 0.6 mmol scale. Yellow oil; yield: 85 mg (65%). IR (neat): 3062, 2962, 2924, 2866, 2223, 1609, 1485, 1471, 1447, 1416, 1302, 1283, 1219, 1077, 1023, 893, 835, 783, 759, 737 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.72 (m, 2 H), 7.69 (s, 1 H), 7.62 (d, J = 7.9 Hz, 1 H), 7.46 (d, J = 7.1 Hz, 1 H), 7.43–7.34 (m, 2 H), 1.48 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ = 154.19, 154.16, 143.8, 137.2, 131.4, 129.1, 127.5, 126.4, 122.9, 121.1, 120.5, 119.7, 110.1, 47.1, 26.8. HRMS (EI); m/z [M]+ calcd for C16H13N: 219.1048; found: 219.1054.
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