A Phosphine-Free Approach to Primary Amides by Palladium-Catalyzed Aminocarbonylation of Aryl and Heteroaryl Iodides Using Methoxylamine Hydrochloride as an Ammonia Equivalent

Abstract

The palladium-catalyzed synthesis of primary amides by aminocarbonylation of aryl and heteroaryl iodides under phosphine-free conditions is reported for the first time. Methoxylamine hydrochloride, acting as an ammonia equivalent, undergoes sequential carbonylation and demethoxylation under mild reaction conditions. The procedure does not require a phosphine ligand and takes place in short reaction times at low temperatures to provide the products in excellent yields.

Key words

amides - carbonylation - palladium - catalysis - phosphine-free - cross-coupling

• References

• 1 Roy S, Roy S, Gribble GW. Tetrahedron 2012; 68: 9867
• 2a Soai K, Ookawa A, Hayashi H. J. Chem. Soc., Chem. Commun. 1983; 668
• 2b Prasad A, Kanth J, Periasamy M. Tetrahedron 1992; 48: 4623
• 3a Bose D, Jayalakshmi B. J. Org. Chem. 1999; 64: 1713
• 3b Chaudhari K, Mahajan U, Bhalerao D, Akamanchi K. Synlett 2007; 2815
• 4 Plummer BF, Menendez M, Songster M. J. Org. Chem. 1989; 54: 718
• 5a Owston NA, Parker AJ, Williams JM. J. Org. Lett. 2007; 9: 73
• 5b Foot JS, Kanno H, Giblin GM. P, Taylor RJ. K. Synlett 2002; 1293
• 6 Morera E, Ortar G. Tetrahedron Lett. 1998; 39: 2835
• 7a Schnyder A, Beller M, Mehltretter G, Nsenda T, Studer M, Indolese AF. J. Org. Chem. 2001; 66: 4311
• 7b Schnyder A, Indolese AF. J. Org. Chem. 2002; 67: 594
• 7c Wan Y, Alterman M, Larhed M, Hallberg A. J. Comb. Chem. 2003; 5: 82
• 8a Wu X.-F, Neumann H, Beller M. Chem. Asian J. 2010; 5: 2168
• 8b Wu X.-F, Schranck J, Neumann H, Beller M. ChemCatChem 2012; 4: 69
• 9 Ueda K, Sato Y, Mori M. J. Am. Chem. Soc. 2000; 122: 10722
• 10a Nielsen DU, Taaning RH, Lindhardt AT, Gøgsig TM, Skrydstrup T. Org. Lett. 2011; 13: 4454
• 10b Wu X, Wannberg J, Larhed M. Tetrahedron 2006; 62: 4665
• 10c Xu T, Alper H. Tetrahedron Lett. 2013; 54: 5496
• 11a Yanase T, Monguchi Y, Sajiki H. RSC Adv. 2012; 2: 590
• 11b Kitamura Y, Sako S, Udzu T, Tsutsui A, Maegawa T, Monguchi Y, Sajiki H. Chem. Commun. 2007; 5069
• 11c Gupte SP, Chaudhari RV. J. Catal. 1988; 114: 246
• 12a Gadge ST, Bhanage BM. J. Org. Chem. 2013; 78: 6793
• 12b Gadge ST, Khedkar MV, Lanke SR, Bhanage BM. Adv. Synth. Catal. 2012; 354: 2049
• 12c Gadge ST, Bhanage BM. Synlett 2013; 24: 981
• 13a Maitlis PM, Haynes A, James BR, Catellanic M, Chiusoli GP. Dalton Trans. 2004; 3409
• 13b Perry RJ, Wilson BD. J. Org. Chem. 1996; 61: 7482
• 14a Graham SL, Scholz TH. Tetrahedron Lett. 1990; 31: 6269
• 14b Labeeuw O, Phansavath P, Genêt J.-P. Tetrahedron Lett. 2004; 45: 7107
• 14c Keck GE, McHardy SF, Murry JA. Tetrahedron Lett. 1993; 34: 6215
• 15 Aminocarbonylation of Aryl and Heteroaryl Iodides; General Procedure To an autoclave (100 mL capacity), were added an aryl halide (1 mmol), methoxylamine hydrochloride (1.2 equiv), DABCO (2 equiv), PdCl₂ (10 mol%), NaI (0.2 mmol) and MeCN (15 mL), under an inert atm. The autoclave was flushed three times with CO and then pressurized to 5 atm of CO. The mixture was stirred with a mechanical stirrer (550 rpm) at 90 °C for 8 h. The reactor was cooled to r.t., degassed carefully, opened and the reaction mixture removed. The reactor vessel was washed with EtOAc (2 × 5 mL) to remove residual product. The mixture was filtered and the filtrate washed with brine (2 × 4 mL), dried over Na₂SO₄, filtered and the solvent evaporated under vacuum. Purification of the residue was carried out by column chromatography (silica gel, 100–200 mesh, PE–EtOAc) to afford the corresponding product in good to excellent yield.
• 16a Gowda RR, Chakraborty D. Eur. J. Org. Chem. 2011; 2226
• 16b Li X.-Q, Wang W.-K, Han Y.-X, Zhang C. Adv. Synth. Catal. 2010; 352: 2588
• 16c Tu T, Wang Z, Liu Z, Feng X, Wang Q. Green Chem. 2012; 14: 921
• 16d Samanta R, Antonchick AP, Bauer JO, Strohmann C. Org. Lett. 2012; 14: 5518