N-Heterocyclic Carbene (NHC)-Catalyzed Tail-to-Tail Dimerization of Acrylamides

Abstract

The tail-to-tail dimerization of acrylamides enables the formation of diamides. However, only one example of N,N-dimethylacrylamide has been described in the literature. Herein, an NHC-catalyzed tail-to-tail dimerization of acrylamides in moderate to excellent yields is presented. In this context, N-arylacrylamides are susceptible to the dimerization reaction, which features high reaction efficiency, good E-selectivity, and easy operation.

Key words

N-heterocyclic carbene - dimerization - acrylamide - dimer - tail-to-tail

Publication History

Received: 30 May 2024

Accepted after revision: 23 July 2024

Article published online:
14 August 2024

• References

• 1a Chauvin Y, Olivier H. In Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 1. Cornils B, Herrmann W. VCH; Weinheim: 1996: 258-268
• 1b Skupinska J. Chem. Rev. 1991; 91: 613

For selected examples of the Ru-catalyzed dimerization of acrylonitrile, see:
• 2a Kashiwagi K, Sugise R, Shimakawa T, Matuura T, Shirai M, Kakiuchi F, Murai S. Organometallics 1997; 16: 2233
• 2b Fukuoka A, Nagano T, Furuta S, Yoshizawa M, Hirano M, Komiya S. Bull. Chem. Soc. Jpn. 1998; 71: 1409
• 2c Kashiwagi K, Sugise R, Shimakawa T, Matuura T, Shirai M. J. Mol. Catal. A: Chem. 2007; 264: 9
• 2d Kashiwagi K, Sugise R, Shimakawa T, Matuura T, Shirai M. Chem. Lett. 2006; 35: 186
• 2e Kashiwagi K, Sugise R, Shimakawa T, Matuura T. Chem. Lett. 2007; 36: 1384
• 2f Kashiwagi K, Sugise R, Shimakawa T, Matuura T, Shirai M. J. Mol. Catal. A: Chem. 2008; 286: 120

For reviews on the dimerization of acrylates, see:
• 3a Parshall GW, Ittel SD. Homogeneous Catalysis: The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes, 2nd ed. Wiley; New York: 1992: 82
• 3b Tembe GL, Bandyopadhyay AR, Ganeshpure PA, Satish S. Catal. Rev.: Sci. Eng. 1996; 38: 299
• 4 Ohgomori Y, Ichikawa S, Sumitani N. Organometallics 1994; 13: 3758
• 5a Kobayashi Y, Taira S. Tetrahedron 1968; 24: 5763
• 5b Higashimura M, Imamura K, Yokogawa Y, Sakakibara T. Chem. Lett. 2004; 33: 728
• 5c Matsuoka S.-i. Polym. J. 2015; 47: 713

For reviews on NHC organocatalysis, see:
• 6a Zeitler K. Angew. Chem. Int. Ed. 2005; 44: 7506
• 6b Marion N, Díez-González S, Nolan SP. Angew. Chem. Int. Ed. 2007; 46: 2988
• 6c Enders D, Niemeier O, Henseler A. Chem. Rev. 2007; 107: 5606
• 6d Rovis T. Chem. Lett. 2008; 37: 2
• 6e Moore JL, Rovis T. Top. Curr. Chem. 2010; 291: 77
• 6f Hirano K, Piel I, Glorius F. Chem. Lett. 2011; 40: 786
• 6g Cohen DT, Scheidt KA. Chem. Sci. 2012; 3: 53
• 6h Mahatthananchai J, Bode JW. Chem. Sci. 2012; 3: 192
• 6i Grossmann A, Enders D. Angew. Chem. Int. Ed. 2012; 51: 314
• 6j Izquierdo J, Hutson GE, Cohen DT, Scheidt KA. Angew. Chem. Int. Ed. 2012; 51: 11686
• 6k Fèvre M, Pinaud J, Gnanou Y, Vignolle J, Taton D. Chem. Soc. Rev. 2013; 42: 2142
• 6l Dai L, Ye S. Chin. Chem. Lett. 2021; 32: 660

For reviews on NHC organocatalysis beyond umpolung, see:
• 7a Biju AT, Kuhl N, Glorius F. Acc. Chem. Res. 2011; 44: 1182
• 7b Vora HU, Wheeler P, Rovis T. Adv. Synth. Catal. 2012; 354: 1617
• 7c Ryan SJ, Candish L, Lupton DW. Chem. Soc. Rev. 2013; 42: 4906
• 7d Mahatthananchai J, Bode JW. Acc. Chem. Res. 2014; 47: 696
• 8 Breslow R. J. Am. Chem. Soc. 1958; 80: 3719
• 9 Fischer C, Smith SW, Powell DA, Fu GC. J. Am. Chem. Soc. 2006; 128: 1472
• 10 Biju AT, Padmanaban M, Wurz NE, Glorius F. Angew. Chem. Int. Ed. 2011; 50: 8412
• 11 Kato T, Matsuoka S.-i, Suzuki M. J. Org. Chem. 2014; 79: 4484
• 12 Schedler M, Wurz NE, Daniliuc CG, Glorius F. Org. Lett. 2014; 16: 3134
• 13 Matsuoka S.-i, Nakazawa M, Suzuki M. Bull. Chem. Soc. Jpn. 2015; 88: 1093
• 14 Rajachan O-a, Paul M, Yatham VR, Neudörfl J.-M, Kanokmedhakul K, Kanokmedhakul S, Berkessel A. Tetrahedron Lett. 2015; 56: 6537
• 15 Hu Y, Wang Z, Luo H, Jin H, Liu Y, Zhou B. Org. Biomol. Chem. 2021; 19: 3834