Copper-Catalyzed Oxidative Cyanation of Aryl Halides with Nitriles Involving Carbon–Carbon Cleavage

Ren-Jie Song; Ji-Cheng Wu; Yu Liu; Guo-Bo Deng; Cui-Yan Wu; Wen-Ting Wei; Jin-Heng Li

doi:10.1055/s-0032-1317191

Synlett, Table of Contents

Synlett 2012; 23(17): 2491-2496
DOI: 10.1055/s-0032-1317191

letter

Copper-Catalyzed Oxidative Cyanation of Aryl Halides with Nitriles Involving Carbon–Carbon Cleavage

Ren-Jie Song

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

,

Ji-Cheng Wu

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

^bKey Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha 410081, P. R. of China, Fax: +86(731)88713642 Email: jhli@hnu.edu.cn

,

Yu Liu

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

,

Guo-Bo Deng

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

,

Cui-Yan Wu

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

^bKey Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha 410081, P. R. of China, Fax: +86(731)88713642 Email: jhli@hnu.edu.cn

,

Wen-Ting Wei

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

,

Jin-Heng Li*

^aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China

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Abstract

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Abstract

A novel, general route for the synthesis of aromatic nitriles is presented that proceeds through Cu(OAc)₂-catalyzed oxidative cyanation of aryl halides using commercially available nitriles as the cyanide sources and Ag₂O/air as the oxidizing agent. It is noteworthy that this work provides a new example of using acetonitrile as the cyanide source for aromatic nitrile synthesis through a Cu-catalyzed oxidative C–C bond cleavage and cyanation process.

Key words

copper - oxidation - cyanation - aryl halides - nitriles

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References

References and Notes

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10 See Figure S1 and Scheme S1 in the Supporting Information for detailed data.
11 Copper-Catalyzed Oxidative Cyanation of Aryl Halides with Nitriles; Typical Procedure: To a Schlenk tube were added aryl halide 1 (0.3 mmol), Cu(OAc)₂ (20 mol%), triphenylphosphine oxide (40 mol%), Ag₂O (1 equiv) and MeCN (1 mL) at room temperature. Then the tube was stirred at 125 °C (thermometer temperature) for the indicated time until complete consumption of starting material was observed (reaction monitored by TLC and GC-MS analysis). Upon completion, the reaction mixture was diluted in diethyl ether and washed with brine. The aqueous phase was re-extracted with diethyl ether. The combined organic extracts were dried over Na₂SO₄ and concentrated under vacuum, and the resulting residue was purified by silica gel column chromatography (hexane–ethyl acetate) to afford the product. 4-Methoxybenzonitrile (3): Yield: 36.3 mg (91%); white solid. ¹H NMR (500 MHz, DMSO-d ₆): δ = 7.76–7.74 (m, 2 H), 7.10–7.08 (m, 2 H), 3.83 (s, 3 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 162.2, 133.6, 118.6, 114.6, 102.3, 55.1. MS (EI, 70 eV): m/z (%) = 133 (100) [M]⁺, 102 (43). See also: Zhou W., Xu J.-J., Zhang L.-R., Jiao. N.; Org. Lett.; 2010, 12: 2888.
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14 During the cyanation of 1-iodo-4-methoxybenzene (1a) with 2-phenylacetonitrile (2b), benzoic acid was observed by GC-MS analysis (about 10% GC yield). Under the present optimal conditions, benzaldehyde can be readily oxidized to benzoic acid.

Supplementary Material

Supporting Information