Copper-Catalysed Hydroamination of N-Allenylsulfonamides: The Key Role of Ancillary Coordinating Groups

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

A copper-catalysed hydroamination reaction of N-allenylsulfonamides with amines has been developed through a rational approach based on mechanistic studies. The reaction is promoted by a simple copper(I) catalyst and proceeds at room temperature with complete regioselectivity and excellent stereoselectivity towards linear (E)-N-(3-aminoprop-1-enyl)sulfonamides. Density Functional Theory (DFT) studies allow interpreting the key role of unsaturated substituents on nitrogen as ancillary coordinating moieties for the copper catalyst.

Key words

hydroamination - N-allenylsulfonamide - copper(I) catalyst - N-(3-aminoprop-1-enyl)sulfonamide - mechanistic study - ancillary coordinating moiety

• References

• 1a Mueller TE, Beller M. Chem. Rev. 1998; 98: 675
• 1b Brunet J.-J, Neibecker D. In Catalytic Hydrofunctionalization . Togni A, Grützmacher H. Wiley-VCH; Weinheim: 2001: 91
• 1c Pohlki F, Doye S. Chem. Soc. Rev. 2003; 32: 104
• 1d Widenhoefer RA, Han X. Eur. J. Org. Chem. 2006; 4555
• 1e Severin R, Doye S. Chem. Soc. Rev. 2007; 36: 1407
• 1f Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem. Rev. 2008; 108: 3795
• 1g Patil NT, Kavthe RD, Shinde VS. Tetrahedron 2012; 68: 8079
• 1h Reznichenko AL, Hultzsch KC. Top. Organomet. Chem. 2013; 43: 51
• 1i Nishina N, Yamamoto Y. Top. Organomet. Chem. 2013; 43: 115
• 1j Huang L, Arndt M, Gooßen K, Heydt H, Gooßen LJ. Chem. Rev. 2015; 115: 2596
• 1k Bernoud E, Lepori C, Mellah M, Schulz E, Hannedouche J. Catal. Sci. Technol. 2015; 5: 2017
• 1l Coman SM, Parvulescu VI. Org. Process Res. Dev. 2015; 19: 1327
• 1m Lepori C, Hannedouche J. Synthesis 2016; 49: 1158
• 1n Hannedouche J. Chimia 2018; 72: 635
• 2 Blieck R, Bahri J, Taillefer M, Monnier F. Org. Lett. 2016; 18: 1482
• 3 Perego LA, Blieck R, Groué A, Monnier F, Taillefer M, Ciofini I, Grimaud L. ACS Catal. 2017; 7: 4253
• 4 Perego LA, Blieck R, Michel J, Ciofini I, Grimaud L, Taillefer M, Monnier F. Adv. Synth. Catal. 2017; 359: 4388
• 5a Mujumdar P, Poulsen S.-A. J. Nat. Prod. 2015; 78: 1470
• 5b Mujumdar P, Teruya K, Tonissen KF, Vullo D, Supuran CT, Peat TS, Poulsen S.-A. J. Med. Chem. 2016; 59: 5462
• 5c Petkowski JJ, Bains W, Seager S. J. Nat. Prod. 2018; 81: 423
• 6a Reitz AB, Smith GR, Parker MH. Expert Opin. Ther. Pat. 2009; 19: 1449
• 6b Kalgutkar AS, Jones R, Sawant A. In Metabolism, Pharmacokinetics, Toxicity of Functional Groups: Impact of Chemical Building Blocks on ADMET . Smith DA. RSC Publishing; Cambridge: 2010: 210
• 7 Chinthakindi PK, Naicker T, Thota N, Govender T, Kruger HG, Arvidsson PI. Angew. Chem. Int. Ed. 2017; 56: 4100
• 8a Supuran CT, Casini A, Scozzafava A. Med. Res. Rev. 2003; 23: 535
• 8b Supuran C, Innocenti A, Mastrolorenzo A, Scozzafava A. Mini-Rev. Med. Chem. 2004; 4: 189
• 8c Winum J.-Y, Scozzafava A, Montero J.-L, Supuran CT. Med. Res. Rev. 2006; 26: 767
• 8d Smith DA, Jones RM. Curr. Opin. Drug Discovery Dev. 2008; 11: 72
• 8e Shoaib Ahmad Shah S, Rivera G, Ashfaq M. Mini-Rev. Med. Chem. 2013; 13: 70
• 8f Ammazzalorso A, De Filippis B, Giampietro L, Amoroso R. Chem. Biol. Drug Des. 2017; 90: 1094
• 9 Bäckvall and co-workers have already observed a similar influence of pendant allyl groups in a copper-catalysed reaction. N-Allyl and N-aryl secondary sulfonamides could be coupled with bromoallenes by the use of a copper catalyst giving N-allenyl-N-allylsulfonamides, but the reaction failed when saturated N-substituents were employed. Persson AK. Å, Johnston EV, Bäckvall J.-E. Org. Lett. 2009; 11: 3814