Synlett 2019; 30(17): 1977-1980
DOI: 10.1055/s-0039-1690026
cluster
© Georg Thieme Verlag Stuttgart · New York

Transfer Hydration of Dinitriles to Dicarboxamides

Asuka Naraoka
a   Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan
,
Hiroshi Naka
b   Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: h_naka@nagoya-u.jp
› Author Affiliations
H.N. is grateful for financial support from the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Number JP17K05859) and Toyota Physical and Chemical Research Institute (Toyota Riken).
Further Information

Publication History

Received: 30 June 2019

Accepted after revision: 04 September 2019

Publication Date:
24 September 2019 (online)


Published as part of the Cluster Metathesis beyond Olefins

Abstract

We present a robust method for double transfer hydration of dinitriles to afford diamides. The transfer hydration of 1,n-dinitriles (n = 1–6) proceeds smoothly in the presence of a palladium(II) catalyst with acetamide as a water donor, affording the corresponding diamides in moderate to high yields, without involving significant side reactions such as monohydration or cyclization. The equilibrium was shifted in the forward direction by removing coproduced acetonitrile under reduced pressure.

Supporting Information

 
  • References and Notes

    • 1a Chen P, Gao M, Wang D.-X, Zhao L, Wang M.-X. J. Org. Chem. 2012; 77: 4063
    • 1b Hu H.-J, Chen P, Ao Y.-F, Wang Q.-Q, Wang D.-X, Wang M.-X. Org. Chem. Front. 2019; 6: 808
    • 2a Gellman SH, Dado GP, Liang G.-B, Adams BR. J. Am. Chem. Soc. 1991; 113: 1164
    • 2b Liang G.-B, Desper JM, Gellman SH. J. Am. Chem. Soc. 1993; 115: 925
    • 3a Ahmed TJ, Knapp SM. M, Tyler DR. Coord. Chem. Rev. 2011; 255: 949
    • 3b García-Álvarez R, Crochet P, Cadierno V. Green Chem. 2013; 15: 46
    • 4a Murahashi S.-I, Sasao S, Saito E, Naota T. Tetrahedron 1993; 49: 8805
    • 4b Chin C.-S, Kim S.-Y, Joo K.-S, Won G, Chong D. Bull. Korean Chem. Soc. 1999; 20: 535
    • 4c Ghaffar T, Parkins AW. J. Mol. Catal. A 2000; 160: 249
    • 4d Goto A, Endo K, Saito S. Angew. Chem. Int. Ed. 2008; 47: 3607
    • 4e Crestani MG, García JJ. J. Mol. Catal. A 2009; 299: 26
    • 4f Kiyota S, Kobori T, Soeta H, Ichikawa Y.-I, Komine N, Komiya S, Hirano M. Polyhedron 2016; 120: 3
    • 4g Tomás-Mendivil E, Francos J, González-Fernández R, González-Liste PJ, Borge J, Cadierno V. Dalton Trans. 2016; 45: 13590
    • 5a Breuilles P, Leclerc R, Uguen D. Tetrahedron Lett. 1994; 35: 1401
    • 5b García-Garrido SE, Francos J, Cadierno V, Basset J.-M, Polshettiwar V. ChemSusChem 2011; 4: 104
    • 6a Tachinami T, Nishimura T, Ushimaru R, Noyori R, Naka H. J. Am. Chem. Soc. 2013; 135: 50
    • 6b Matsuoka A, Isogawa T, Morioka Y, Knappett BR, Wheatley AE. H, Saito S, Naka H. RSC Adv. 2015; 5: 12152
    • 6c Ushimaru R, Nishimura T, Iwatsuki T, Naka H. Chem. Pharm. Bull. 2017; 65: 1000
  • 7 Kanda T, Naraoka A, Naka H. J. Am. Chem. Soc. 2019; 141: 825

    • For Pd-catalyzed conversion of nitriles with amides, see:
    • 8a Maffioli SI, Marzorati E, Marazzi A. Org. Lett. 2005; 7: 5237
    • 8b Dubey P, Gupta S, Singh AK. Dalton Trans. 2017; 46: 13065
  • 9 For acceptor-controlled transfer dehydration of amides, see: Okabe H, Naraoka A, Isogawa T, Oishi S, Naka H. Org. Lett. 2019; 21: 4767
    • 10a Noyori R, Hashiguchi S. Acc. Chem. Res. 1997; 30: 97
    • 10b Bhawal BN, Morandi B. Angew. Chem. Int. Ed. 2019; 58: 10074
  • 11 Reactor A was used throughout the experiments unless otherwise noted.
  • 12 Typical Procedure for Double Transfer Hydration To a 500 mL round-bottom flask equipped with a stirring bar and a 2-necked Teflon stopcock were added glutaronitrile (1a, 942.1 mg, 10.0 mmol), acetamide (5900.5 mg, 99.9 mmol), and acetic acid (20 mL). The mixture was stirred at 50 °C for 30 min under open air (760 mmHg). Pd(CH3CN)4(BF4)2 (4.52 mg, 0.0102 mmol) was added to start the reaction, and the mixture was stirred at 50 °C for 2 h under reduced pressure (1–3 mmHg). The internal pressure was continuously reduced by means of a belt drive rotary vane vacuum pump (SATO VAC INC. USW-50) equipped with a 450 mL liq. nitrogen trap (for acetonitrile and acetic acid). The resulting pale-yellow crude mixture was washed with acetonitrile (50 mL) with sonication for 1 h to remove acetamide. The precipitate was collected by filtration on a membrane filter (Merck Millipore JHWP04700 0.45 μm pore size, hydrophilic PTFE membrane, 47 mm diameter) and dried in vacuo at 120 °C overnight to afford glutaramide (2a, 1043.3 mg, 80% yield) with minor contamination with acetamide (27.0 mg, as determined by 1H NMR spectroscopy). The product (499.7 mg) was recrystallized from methanol to give analytically pure 2a (418.9 mg, 69% overall yield).
  • 13 Analytical Data of Selected Products Compound 2a: white solid; mp 181–182 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 1.67 (quin, J = 7.6 Hz, 2 H), 2.03 (t, J = 7.6 Hz, 4 H), 6.69 (br s, 2 H), 7.24 (br s, 2 H). 13C{1H} NMR (150 MHz, DMSO-d 6): δ = 21.3, 34.6, 174.5. IR (KBr): 3381 (NH), 3190 (NH), 1650 (CO) cm–1. HRMS (FAB): m/z calcd for [C5H10N2O2Na+] [M + Na+]: 153.0640; found: 153.0633. Compound 2d: white solid; mp 153–154 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 0.98 (d, J = 6.9 Hz, 3 H), 1.45–1.51 (m, 1 H), 1.62–1.69 (m, 1 H), 1.95–2.09 (m, 2 H), 2.19 (sext, J = 6.9 Hz, 1 H), 6.69 (br s, 2 H), 7.23 (br s, 2 H). 13C{1H} NMR (150 MHz, DMSO-d 6): δ = 17.8, 29.3, 32.9, 39.0, 174.0, 177.5. IR (KBr): 3396 (NH), 3210 (NH), 1660 (CO) cm–1. HRMS (FAB): m/z calcd for [C6H12N2O2Na+] [M + Na+]: 167.0796; found: 167.0796. Compound 2e: white solid; mp 157–159 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 2.16–2.17 (m, 4 H), 4.15 (dquin, J = 6.1, 4.8 Hz, 1 H), 4.87 (d, J = 4.8 Hz, 1 H), 6.81 (br s, 2 H), 7.28 (br s, 2 H). 13C{1H} NMR (150 MHz, DMSO-d 6): δ = 42.8, 65.1, 172.8. IR (KBr): 3411 (NH), 3184 (NH), 1651 (CO) cm–1. HRMS (FAB): m/z calcd for [C5H10N2O3Na+] [M + Na+]: 169.0589; found: 169.0581. Compound 2f: white solid; mp decomp. >150 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 3.59 (s, 2 H), 6.99 (br s, 1 H), 7.27–7.30 (m, 2 H), 7.38 (dt, J = 7.6, 1.4 Hz, 1 H), 7.43 (br s, 1 H), 7.47 (dd, J = 7.9, 1.7 Hz, 1 H), 7.68 (br s, 1 H), 8.22 (br s, 1 H). 13C{1H} NMR (150 MHz, DMSO-d 6): δ = 39 (overlapped with DMSO-d 6), 126.4, 128.0, 129.6, 130.4, 134.0, 136.8, 170.7, 172.8. IR (KBr): 3394 (NH), 3195 (NH), 1650 (CO) cm–1. HRMS (FAB): m/z calcd for [C9H10N2O2Na+] [M + Na+]: 201.0640; found: 201.0632.