Efficient Pd-Catalyzed Hydrodehalogenation of o-Haloanilides in Water

^◊ These authors contributed equally to this work

Abstract

In the present work, we have developed a practical methodology for the hydrodehalogenation of o-haloanilides using PdCl₂ at 100 °C under mild conditions in water. The catalytic system could selectively dehalogenate both aryl chloride and aryl bromide and exhibit a broad functional group tolerance.

Key words

Pd-catalyzed - dppap - hydrodehalogenation - o-haloanilides - water

• References and Notes

• 1 Smith MB, March J. March’s Advanced Organic Chemistry: Reactions, Mechanisms and Structure, 5th ed. Wiley-Interscience; New York: 2001
• 2 Jouha J, Khouili M, Hiebel MA, Guillaumet G, Suzenet F. Tetrahedron Lett. 2018; 59: 3108
• 3 Grushin VV, Alper H. Chem. Rev. 1994; 94: 1047
• 4 Parveen I, Khan D, Ahmed N. Eur. J. Org. Chem. 2019; 759
• 5 You T, Wang Z, Chen J, Xia Y. J. Org. Chem. 2017; 82: 1340
• 6 Marozsán N, Horváth H, Erdei A, Joó F. J. Mol. Catal. A: Chem. 2016; 425: 103
• 7a Jouha J, Khouili M, Hiebel MA, Guillaumet G, Suzenet F. Tetrahedron Lett. 2018; 59: 3108
• 7b Hirasawa N, Takahashi Y, Fukuda E, Sugimoto O, Tanji K. Tetrahedron Lett. 2008; 49: 1492
• 7c Kara BY, Yazici M, Kilbas B, Goksu H. Tetrahedron 2016; 72: 5898
• 7d Moon J, Lee S. J. Org. Chem. 2009; 694: 473
• 8a Francisco A, Irina PB, Miguel Y. Chem. Rev. 2002; 102: 4009
• 8b Xue FL, Qi J, Peng P, Mo GZ, Wang ZY. Lett. Org. Chem. 2014; 11: 64
• 9 Chen J, Zhang Y, Yang L, Zhang X, Liu J, Li L, Zhang H. Tetrahedron 2007; 63: 4266
• 10 Bhattacharjya A, Klumphu P, Lipshutz BH. Org. Lett. 2015; 17: 1122
• 11 Viciu MS, Grasa GA, Nolan SP. Organometallics 2001; 20: 3607
• 12a Chan SK, Liu RC, Wong LK. Tetrahedron Lett. 2015; 56: 2728
• 12b Adimurthy S, Ramachandraiah G. Tetrahedron Lett. 2004; 45: 5251
• 12c Inoue K, Sawada A, Shibata I, Baba A. J. Am. Chem. Soc. 2002; 124: 906
• 12d Chelucci G, Baldino S, Ruiu A. J. Org. Chem. 2012; 77: 9921
• 12e Chelucci G, Baldino S, Pinna GA, Pinna G. Curr. Org. Chem. 2012; 16: 2921
• 13a Sasmal S, Sen I, Hall RG, Pal S. Tetrahedron Lett. 2015; 56: 1374
• 13b Cheng Y, Peng Q, Fan W, Li P. J. Org. Chem. 2014; 79: 5812
• 13c Kee CH, Ariffin A, Awang K, Takeya K, Morita H, Hussain SI, Chan KM, Wood PJ, Threadgill MD, Lim CG, Ng S, Weber JF. F, Thomas NF. Org. Biomol. Chem. 2010; 8: 5646
• 14 Tang Y, Li M, Gao H, Rao G, Mao Z. RSC Adv. 2020; 10: 14317
• 15 General Procedure for Hydrodehalogenation of o-Haloanilides To a stirred solution of o-haloanilide (1 mmol), PdCl₂ (3.6 mg, 0.02 mmol), Et₃N (202 mg, 2 mmol), and dppap (8.5 mg, 0.05 mmol) in water (5 mL) at 100 °C for 12 h. After completion of the reaction (indicated by TLC), the mixture was filtered, and the filtrate was extracted with EtOAc (2 × 5 mL). The organic layer was dried by anhydrous Na₂SO₄, concentrated in vacuo, and the residue was isolated by column chromatography (PE/EtOAc, 5:1) to afford the respective products. N-Phenylacetamide (2a) Prepared according to the general procedure from 1aa as a white solid (mp 111–113 °C); yield: 116 mg (86%). ¹H NMR (400 MHz, CDCl₃): δ = 8.34 (s, 1 H), 7.44 (d, J = 7.8 Hz, 2 H), 7.21 (t, J = 7.7 Hz, 2 H), 7.02 (t, J = 5.3 Hz, 1 H), 2.06 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.34, 138.04, 128.94, 124.44, 120.36, 24.33.