Palladium-Catalyzed Carbonylation of Azides and Mechanistic Studies

Abstract

Isocyanates are widely applied in the fields of materials science, drug discovery and chemical industry processes. Palladium-catalyzed carbonylation of azides with carbon monoxide (CO) is reported as a powerful method for simple and efficient access to isocyanates, which are important precursors for preparing structurally meaningful urea, carbamate and amidine derivatives. In this account, we provide an overview on the synthesis of isocyanates and their subsequent reactions to obtain diverse nucleophilic addition products. In addition, with particular emphasis on our mechanistic studies of the Pd-catalyzed carbonylation process, we outline the identification of the actual catalytic species, the possible intermediates and some key factors in the catalytic cycle.

1 Introduction

2 Palladium-Catalyzed Reaction of Azides with CO and Subsequent Nucleophilic Additions

3 Mechanistic Studies on the Palladium-Catalyzed Reaction of Azides with CO

3.1 Studies on the Actual Catalytic Species and the Key Intermediates in the Activation and Carbonylation of Acyl Azides

3.2 Study of the Sulfonylurea Product Self-Catalyzed Carbonylation of Sulfonyl Azides

3.3 Study of the Actual Catalytic Pattern of the Pd/C Catalyst

4 Conclusion

Key words

azides - isocyanates - palladium catalysts - carbon monoxide - ureas

• References

• 1a Braunstein P, Nobel D. Chem. Rev. 1989; 89: 1927
• 1b Rigby JH. Synlett 2000; 1
• 1c Varela JA, Saa C. Chem. Rev. 2003; 103: 3787
• 1d Allen AD, Tidwell TT. Chem. Rev. 2013; 113: 7287
• 1e Delebecq E, Pascault JP, Boutevin B, Ganachaud F. Chem. Rev. 2013; 113: 80
• 2a Slocombe RJ, Hardy EE, Saunders JH, Jenkins RL. J. Am. Chem. Soc. 1950; 72: 1888
• 2b Eckert H, Forster B. Angew. Chem. Int. Ed. 1987; 26: 894
• 3 Shi F. J. Catal. 2003; 219: 372
• 4 Buchner E, Curtius T. Chem. Ber. 1885; 18: 2371
• 5 Hofmann AW. Ber. Dtsch. Chem. Ges. 1881; 14: 2725
• 6 Lossen W. Liebigs Ann. Chem. 1869; 150: 313
• 7 Collman JP, Kubota M, Hosking JW. J. Am. Chem. Soc. 1967; 89: 4809
• 8 Bennett RP, Hardy WB. J. Am. Chem. Soc. 1968; 90: 3295
• 9a Doi H, Barletta J, Suzuki M, Noyori R, Watanabe Y, Langstrom B. Org. Biomol. Chem. 2004; 2: 3063
• 9b Åberg O, Långström B. J. Comb. Chem. 2011; 54: 38
• 10a Handbook of Organopalladium Chemistry for Organic Synthesis. Negishi E. John Wiley & Sons; New York: 2002
• 10b Tsuji J. Palladium Reagents and Catalysts: New Perspectives for the 21st Century. John Wiley & Sons; Chichester: 2004
• 10c Xiao Q, Zhang Y, Wang J. Acc. Chem. Res. 2013; 46: 236
• 10d Wu X.-F, Neumann H, Beller M. Chem. Soc. Rev. 2011; 40: 4986
• 11a Zhang Z, Liu Y, Gong M, Zhao X, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2010; 49: 1139
• 11b Zhou P.-X, Zhou Z.-Z, Chen Z.-S, Ye Y.-Y, Zhao L.-B, Yang Y.-F, Xia X.-F, Luo J.-Y, Liang Y.-M. Chem. Commun. 2013; 49: 561
• 11c Liu Y, Zhang Z, Zhang S, Zhang Y, Wang J, Zhang Z. Chem. Asian J. 2018; 13: 3658
• 12a Zhang Z, Liu Y, Ling L, Li Y, Dong Y, Gong M, Zhao X, Zhang Y, Wang J. J. Am. Chem. Soc. 2011; 133: 4330
• 12b Zhang Z, Zhang Y, Wang J. ACS Catal. 2011; 1: 1621
• 13 Miloserdov FM, Grushin VV. Angew. Chem. Int. Ed. 2012; 51: 3668
• 14 Ren L, Jiao N. Chem. Commun. 2014; 50: 3706
• 15 Izzo AA, Ernst E. Drugs 2009; 69: 1777
• 16 Lentza-Rizos C, Balokas A. J. Agric. Food Chem. 2001; 49: 710
• 17 Zhao J, Li Z, Song S, Wang MA, Fu B, Zhang Z. Angew. Chem. Int. Ed. 2016; 55: 5545
• 18 Li Z, Xu S, Huang B, Yuan C, Chang W, Fu B, Jiao L, Wang P, Zhang Z. J. Org. Chem. 2019; 84: 9497
• 19 Zhao J, Li Z, Yan S, Xu S, Wang MA, Fu B, Zhang Z. Org. Lett. 2016; 18: 1736
• 20a Zhang CL, Katoh M, Shibasaki T, Minami K, Sunaga Y, Takahashi H, Yokoi N, Iwasaki M, Miki T, Seino S. Science 2009; 325: 607
• 20b Guan A, Liu C, Yang X, Dekeyser M. Chem. Rev. 2014; 114: 7079
• 21a Chow SY, Stevens MY, Odell LR. J. Org. Chem. 2016; 81: 2681
• 21b Chow SY, Odell LR. J. Org. Chem. 2017; 82: 2515
• 21c Schembri LS, Eriksson J, Odell LR. J. Org. Chem. 2019; 84: 6970
• 21d Mozaffari M, Nowrouzi N. Eur. J. Org. Chem. 2019; 46: 7541
• 22 Chen B, Peng JB, Ying J, Qi X, Wu X.-F. Adv. Synth. Catal. 2018; 360: 4585
• 23 Wang L, Wang H, Li G, Min S, Xiang F, Liu S, Zheng W. Adv. Synth. Catal. 2018; 360: 2820
• 24 Karmouta MG, Miocque M, Derdour A, Gayral P, Lafont O. Eur. J. Med. Chem. 1989; 24: 547
• 25 Willcox D, Chappell BG, Hogg KF, Calleja J, Smalley AP, Gaunt MJ. Science 2016; 354: 851
• 26a Mindiola DJ, Hillhouse GL. J. Am. Chem. Soc. 2001; 123: 4623
• 26b Jenkins DM, Betley TA, Peters JC. J. Am. Chem. Soc. 2002; 124: 11238
• 26c Scepaniak JJ, Bontchev RP, Johnson DL, Smith JM. Angew. Chem. Int. Ed. 2011; 50: 6630
• 27a Badiei YM, Krishnaswamy A, Melzer MM, Warren TH. J. Am. Chem. Soc. 2006; 128: 15056
• 27b Laskowski CA, Hillhouse GL. Organometallics 2009; 28: 6114
• 28 Cenini S, Gallo E, Caselli A, Ragaini F, Fantauzzi S, Piangiolino C. Coord. Chem. Rev. 2006; 250: 1234
• 29a Besenyei G, Párkányi L, Foch L, Simándi LI, Kálmán A. Chem. Commun. 1997; 12: 1143
• 29b Besenyei G, Párkányi L, Szalontai G, Holly S, Pápai I, Keresztury G, Nagy A. Dalton Trans 2004; 13: 2041
• 30 All calculations were performed using the Gaussian 09 program. The density functional theory (DFT) formalism with the B3LYP functional and LanL2DZ mixed basis sets for Pd atoms and the 6-31G(d,p) basis sets for other main group atoms were applied. Thermodynamic parameters including the Gibbs free energies at 298 K were obtained by frequency calculations. Transition states are realized by the presence of a single negative frequency. The electronic energies of the optimized structures were further corrected by single-point calculations of the M06-D3 functionals with SDD for Pd atoms and 6-311+G(d,p) for other atoms. Single-point solvation energy corrections in THF computed by the ief-PCM method were added to the gas-phase free energy.
• 31 Heidenreich RG, Krauter JG. E, Pietsch J, Köhler K. J. Mol. Catal. A: Chem. 2002; 182–183: 499