Nitrile Hydration Reaction Using Copper Iodide/Cesium Carbonate/DBU in Nitromethane–Water

Abstract

The catalytic nitrile hydration (amide formation) in a copper iodide/cesium carbonate/1,8-diazabicyclo[5.4.0]undec-7-ene/nitromethane–water system is described. The protocol is robust and reliable; it can be applied to a broad range of substrates with high chemoselectivity.

Key words

catalysis - copper iodide - nitrile hydration - nitromethane–water - primary amides

• References and Notes

• 1a García-Álvarez R. Crochet P. Cadierno V. Green Chem. 2013; 15: 46
• 1b Kukushkin VY. Pombeiro AJ. L. Inorg. Chim. Acta 2005; 358: 1
• 2a Andries K. Verhasselt P. Guillemont J. Gohlmann HW. H. Neefs J.-M. Winkler H. Van Gestel J. Timmerman P. Zhu M. Lee E. Williams P. de Chaffoy D. Huitric E. Lounis N. Jarlier V. Science 2005; 307: 223
• 2b Caminero JA. Sotgiu G. Zumla A. Migliori GB. Lancet Infect. Dis. 2010; 10: 621
• 2c Zumla A. Nahid P. Cole ST. Nat. Rev. Drug Discovery 2013; 12: 388
• 2d Battilocchio C. Hawkins JM. Ley SV. Org. Lett. 2014; 16: 1060
• 3 Carey JS. Laffan D. Thomson C. Williams MT. Org. Biomol. Chem. 2006; 4: 2337
• 4 Acid- and baes-promoted hydrolysis of nitriles to amides: Benz G. Synthesis of Amides and Related Compounds. In Comprehensive Organic Synthesis . Vol 6. Trost BM. Fleming I. Winterfeldt E. Pergamon Press; Oxford: 1991: 381
• 5a Murahashi S.-I. Naota T. Saito E. J. Am. Chem. Soc. 1986; 108: 7846
• 5b Mori K. Yamaguchi K. Mizukami T. Ebitani K. Kaneda K. Chem. Commun. 2001; 461
• 5c Cadierno V. Francos J. Gimeno J. Chem. Eur. J. 2008; 14: 6601
• 5d Polshettiwar V. Varma RS. Chem. Eur. J. 2009; 15: 1582
• 5e Baig RB. N. Varma RS. Chem. Commun. 2012; 48: 6220
• 5f Garcia-Álvarez R. Díez J. Crochet P. Cadierno V. Organometallics 2011; 30: 5442
• 5g Lee W.-C. Frost BJ. Green Chem. 2012; 14: 62
• 5h Tomás-Mendivil E. Suarez FJ. Diez J. Cadierno V. Chem. Commun. 2014; 50: 9661
• 5i Tomás-Mendivil E. Cadierno V. Menéndez MI. López R. Chem. Eur. J. 2015; 21: 16874

Cu(0):
• 6a Ravindranathan M. Kalyanam N. Sivaram S. J. Org. Chem. 1982; 47: 4812

CuI in pure water:
• 6b Li Z. Wang L. Zhou X. Adv. Synth. Catal. 2012; 354: 584

C–H activation/amidation:
• 6c Xie W. Yoon JH. Chang S. J. Am. Chem. Soc. 2016; 138: 12605

Review:
• 7a Taylor RJ. K. Reid M. Foot J. Raw SA. Acc. Chem. Res. 2005; 38: 851
• 7b Liu KT. Shih M.-H. Huang H.-W. Hu C.-J. Synthesis 1988; 715
• 7c Yamaguchi K. Wang Y. Kobayashi H. Mizuno N. Chem. Lett. 2012; 41: 574
• 7d Yamaguchi K. Wang Y. Mizuno N. Chem. Lett. 2012; 41: 633
• 8a Subramanian T. Pitchumani K. Catal. Commun. 2012; 29: 109
• 8b Singh K. Sarbajna A. Dutta I. Pandey P. Bera JK. Chem. Eur. J. 2017; 23: 7761
• 9a Hirano T. Uehara K. Kamata K. Mizuno N. J. Am. Chem. Soc. 2012; 134: 6425
• 9b Shimizu K. Kubo T. Satsuma A. Kamachi T. Yoshizawa K. ACS Catal. 2012; 2: 2467
• 10a Ahmed TJ. Fox BR. Knapp SM. M. Yelle RB. Juliette JJ. Tyler DR. Inorg. Chem. 2009; 48: 7828
• 10b Breno KL. Pluth MD. Tyler DR. Organometallics 2003; 22: 1203
• 11a Ramón RS. Marion N. Nolan SP. Chem. Eur. J. 2009; 15: 8695
• 11b Liu Y.-M. He L. Wang M.-M. Cao Y. He H.-Y. Fan K.-N. ChemSusChem 2012; 5: 1392
• 11c Mitsudome T. Mikami Y. Mori H. Arita S. Mizugaki T. Jitsukawa K. Kaneda K. Chem. Commun. 2009; 45: 3258
• 12 Tamura M. Wakasugi H. Shimizu K. Satsuma A. Chem. Eur. J. 2011; 17: 11428
• 13 Marcé P. Lynch J. Blacker AJ. Williams JM. J. Chem. Commun. 2016; 52: 1436
• 14 Kuwabara J. Sawada Y. Yoshimatsu M. Org. Lett. 2018; 20: 1130
• 15 Tamura M. Sawabe K. Tomishige K. Satsuma A. Shimizu K. ACS Catal. 2015; 5: 20
• 16 Nitrile hydration without water; selective nitrile hydration to amides for p-carbomethoxybenzamide: Kang D. Lee J. Lee H.-Y. Org. Synth. 2012; 89: 66
• 17 Typical Procedure for the Nitrile Hydration of Tolunitrile (1a) To a nitromethane (0.10 mL) solution of 4-methylbenzonitrile (1a, 30 mg, 0.256 mmol) were added H₂O (1.0 mL), DBU (78 mg, 0.512 mmol), copper(I) iodide (9.8 mg, 0.0512 mmol), and cesium(I) carbonate (42 mg, 0.128 mmol) at room temperature. The reaction mixture was heated at 100 °C for 1 h and then poured into water (50 mL). The organic layer was separated, and the aqueous layer was extracted with AcOEt. The combined organic layer was dried over MgSO₄. The solvent was removed under reduced pressure. The residue was purified by preparative TLC on silica gel eluting with AcOEt–n-hexane (1:1) to give 4-methylbenzamide (2a, 32 mg, 92%) as pale yellow powders. ¹H NMR (400 MHz, CDCl₃): δ = 2.40 (3 H, s, CH₃), 6.10 (2 H, br s, NH), 7.25 (2 H, d, J = 8.2 Hz, ArH), 7.71 (2 H, d, J = 8.2 Hz, ArH).