Silver-Catalyzed Synthesis of Nitriles from Carboxylic Acids and Cyanamides

Abstract

A concise and practical silver-catalyzed nitrogen-atom-transfer protocol was developed to access versatile nitriles from ubiquitous carboxylic acids with N-cyano-N-phenyl-p-toluenesulfonamide. This protocol complements the established carboxylic acids-to-nitriles conversion methods, which suffer from laborious steps, high temperatures (≥200 °C), or limited substrate scopes. This approach operates broadly across diverse aryl, alkenyl, and primary-, secondary-, or tertiary-alkyl carboxylic acids.

Key words

carboxylic acids - nitriles - silver - cyanamide - decarboxylation

Publication History

Received: 10 February 2023

Accepted after revision: 13 March 2023

Accepted Manuscript online:
13 March 2023

Article published online:
12 April 2023

• References and Notes

• 1a Enders D, Shilvock JP. Chem. Soc. Rev. 2000; 29: 359
• 1b Fleming FF, Wang Q. Chem. Rev. 2003; 103: 2035
• 1c Lindsay-Scott PJ, Gallagher PT. Tetrahedron Lett. 2017; 58: 2629
• 1d Pearson-Long MS. M, Boeda F, Bertus P. Adv. Synth. Catal. 2017; 359: 179
• 1e An BK, Gierschner J, Park SY. Acc. Chem. Res. 2012; 45: 544
• 1f Chen Y, Peng Z, Tao Y, Wang Z, Lu P, Wang Y. Dyes Pigm. 2019; 161: 44
• 1g Jimenez ER, Rodríguez H. J. Mater. Sci. 2020; 55: 1366
• 1h Lin S, Gutierrez-Cuevas KG, Zhang X, Guo J, Li Q. Adv. Funct. Mater. 2020; 31: 2007957
• 2a Fleming FF. Nat. Prod. Rep. 1999; 16: 597
• 2b Ertl P, Altmann E, McKenna JM. J. Med. Chem. 2020; 63: 8408
• 2c Fleming FF, Yao L, Ravikumar PC, Funk L, Shook BC. J. Med. Chem. 2010; 53: 7902
• 2d Yu H, Cheng Y, Xu M, Song Y, Luo Y, Li B. J. Agric. Food Chem. 2016; 64: 9586
• 3a Demko ZP, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2113
• 3b Garduño JA, García JJ. ACS Catal. 2020; 10: 8012
• 4a Wang T, Jiao N. Acc. Chem. Res. 2014; 47: 1137
• 4b Ping Y, Ding Q, Peng Y. ACS Catal. 2016; 6: 5989
• 4c Yan G, Zhang Y, Wang J. Adv. Synth. Catal. 2017; 359: 4068
• 4d Wu W.-B, Yu J.-S, Zhou J. ACS Catal. 2020; 10: 7668
• 5a Hodgson HH. Chem. Rev. 1947; 40: 251
• 5b Rosenmund KW, Struck E. Ber. Dtsch. Chem. Ges. 2006; 52: 1749
• 6 Mowry DT. Chem. Rev. 1948; 42: 189
• 7a Anbarasan P, Schareina T, Beller M. Chem. Soc. Rev. 2011; 40: 5049
• 7b Delcaillau T, Woenckhaus-Alvarez A, Morandi B. Org. Lett. 2021; 23: 7018
• 8a Anbarasan P, Neumann H, Beller M. Angew. Chem. Int. Ed. 2011; 50: 519
• 8b Reeves JT, Malapit CA, Buono FG, Sidhu KP, Marsini MA, Sader CA, Fandrick KR, Busacca CA, Senanayake CH. J. Am. Chem. Soc. 2015; 137: 9481
• 8c Malapit CA, Reeves JT, Busacca CA, Howell AR, Senanayake CH. Angew. Chem. Int. Ed. 2016; 55: 326
• 9a Shi S, Szostak M. Org. Lett. 2017; 19: 3095
• 9b Chatupheeraphat A, Liao HH, Lee SC, Rueping M. Org. Lett. 2017; 19: 4255
• 9c Wang Z, Wang X, Ura Y, Nishihara Y. Org. Lett. 2019; 21: 6779
• 10a Zhao W, Montgomery J. J. Am. Chem. Soc. 2016; 138: 9763
• 10b Long J, Yu R, Gao J, Fang X. Angew. Chem. Int. Ed. 2020; 59: 6785
• 10c Xing Y, Yu R, Fang X. Org. Lett. 2020; 22: 1008
• 11a Wang T, Jiao N. J. Am. Chem. Soc. 2013; 135: 11692
• 11b Ren Y.-L, Liu W, Zheng Y, Tian X. Synlett 2022; 33: 376
• 12 Hua M, Song J, Huang X, Liu H, Fan H, Wang W, He Z, Liu Z, Han B. Angew. Chem. Int. Ed. 2021; 60: 21479
• 13a McManus JB, Nicewicz DA. J. Am. Chem. Soc. 2017; 139: 2880
• 13b Chen H, Mondal A, Wedi P, van Gemmeren M. ACS Catal. 2019; 9: 1979
• 13c Xu S, Teng J, Yu J.-T, Sun S, Cheng J. Org. Lett. 2019; 21: 9919
• 14a Liu RY, Bae M, Buchwald SL. J. Am. Chem. Soc. 2018; 140: 1627
• 14b Shipilovskikh SA, Vaganov VY, Denisova EI, Rubtsov AE, Malkov AV. Org. Lett. 2018; 20: 728
• 14c Al-Huniti MH, Rivera-Chávez J, Colón KL, Stanley JL, Burdette JE, Pearce CJ, Oberlies NH, Croatt MP. Org. Lett. 2018; 20: 6046
• 14d Fang W.-Y, Qin H.-L. J. Org. Chem. 2019; 84: 5803
• 14e Meng H, Gao S, Luo M, Zeng X. Eur. J. Org. Chem. 2019; 2019: 4617
• 15a Barton DH. R, Jaszberenyi JC, Theodorakis EA. Tetrahedron 1992; 48: 2613
• 15b Wang D, Zhu N, Chen P, Lin Z, Liu G. J. Am. Chem. Soc. 2017; 139: 15632
• 15c Zhong B, Huang H, Jing X, Duan C. Chem. Commun. 2022; 58: 3961
• 16a Ouchaou K, Georgin D, Taran F. Synlett 2010; 2083
• 16b Loreau O, Georgin D, Taran F, Audisio D. J. Labelled Compd. Radiopharm. 2015; 58: 425
• 16c Fu Z, Li Z, Song Y, Yang R, Liu Y, Cai H. J. Org. Chem. 2016; 81: 2794
• 16d Song F, Salter R, Chen L. J. Org. Chem. 2017; 82: 3530
• 16e Fu Z, Cao X, Wang S, Guo S, Cai H. Org. Biomol. Chem. 2020; 18: 8381
• 16f Le Vaillant F, Wodrich MD, Waser J. Chem. Sci. 2017; 8: 1790
• 16g Ramirez NP, König B, Gonzalez-Gomez JC. Org. Lett. 2019; 21: 1368
• 17a Mekki-Berrada A, Bennici S, Gillet J.-P, Couturier J-L, Dubois J.-L, Auroux A. ChemSusChem 2013; 6: 1478
• 17b Mekki-Berrada A, Bennici S, Gillet J.-P, Couturier J.-L, Dubois J.-L, Auroux A. J. Catal. 2013; 306: 30
• 17c Shirazi Y, Tafazolian H, Viamajala S, Varanasi S, Song Z, Heben MJ. ACS Omega 2017; 2: 9013
• 18a Toland WG, Ferstandig LL. J. Org. Chem. 1958; 23: 1350
• 18b Klein DA. J. Org. Chem. 1971; 36: 3050
• 18c Cantillo D, Kappe CO. J. Org. Chem. 2013; 78: 10567
• 18d Cartigny D, Dos Santos A, El Kaïm L, Grimaud L, Jacquot R, Marion P. Synthesis 2014; 46: 1802
• 18e Vanoye L, Hammoud A, Gérard H, Barnes A, Philippe R, Fongarland P, de Bellefon C, Favre-Réguillon A. ACS Catal. 2019; 9: 9705
• 19a Shen Z, Liu W, Tian X, Zhao Z, Ren Y.-L. Synlett 2020; 31: 1805
• 19b Xing A.-P, Shen Z, Zhao Z, Tian X, Ren Y.-L. Catal. Commun. 2021; 149: 106175
• 19c Zhang G, Zhang C, Tian Y, Chen F. Org. Lett. 2023; 25: 917
• 20 Yu D.-G, Gensch T, de Azambuja F, Vásquez-Cespedes S, Glorius F. J. Am. Chem. Soc. 2014; 136: 17722
• 21a Wang Z, Zhu L, Yin F, Su Z, Li Z, Li C. J. Am. Chem. Soc. 2012; 134: 4258
• 21b Tan X, Song T, Wang Z, Chen H, Cui L, Li C. Org. Lett. 2017; 19: 1634
• 22 Mumm O. Ber. Dtsch. Chem. Ges. 1910; 43: 886; DOI: DOI: 10.1002/cber.191004301151.
• 23 4-Methoxybenzonitrile (3a): Typical ProcedureIn an argon-filled glovebox, an oven-dried 4 mL vial equipped with a magnetic stirrer bar was charged with AgSbF₆ (3.4 mg, 5.0 mol%), 4-methoxybenzoic acid (1a, 0.2 mmol, 1.0 equiv), and NCTS (2, 65 mg, 0.24 mmol, 1.2 equiv). Toluene (600 μL) and dodecane (10 μL; internal standard) were added, and the vial was sealed and transferred out of the glove box. The mixture was stirred at 120 ℃ for 48 h, then cooled to r.t. The crude product was purified by column chromatography [silica gel, PE–EtOAc (10:1)] to give a white solid; yield: 79%.¹H NMR (400 MHz, CDCl₃): δ = 7.60–7.56 (m, 2 H), 6.97–6.92 (m, 2 H), 3.85 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 162.9, 134.1, 119.3, 114.8, 104.1, 55.6. HRMS-ESI: m/z [M + H]⁺ calcd for C₈H₈NO: 134.0600; found: 134.0596