Synthesis of Diarylacetylenes Bearing Electron-Withdrawing Groups via the Smiles Rearrangement

Abstract

Nitrobenzyl benzothiazol-2-yl sulfones and nitrobenzyl 1-phenyl-1H-tetrazol-5-yl sulfones react with chlorides of aromatic acids to form β-acyl derivatives. These products undergo the Smiles rearrangement resulting in the formation of the corresponding nitrophenyl arylacetylenes in 50–60% overall yields (approx. 75% per step). Sulfones bearing CF₃ or CN groups instead of a NO₂ substituent form mixtures of the acetylenes in moderate yields and benzyl aryl ketones in yields above 40%.

Key words

acetylenes - sulfones - Smiles rearrangement - Julia–Kocienski olefination - benzyl ketones

• References

• 1a Wang H, Li Y, Jiang L, Zhang R, Jin K, Zhao D, Duan C. Org. Biomol. Chem. 2011; 9: 4983
• 1b Inamoto K, Asano N, Nakamura Y, Yonemoto M, Kondo Y. Org. Lett. 2012; 14: 2622
• 1c McNulty J, Keskar K. Eur. J. Org. Chem. 2014; 8: 1622
• 1d Hiroya K, Itoh S, Sakamoto T. J. Org. Chem. 2004; 69: 1126
• 1e Janreddy D, Kavala V, Kuo C.-W, Kuo T.-S, He C.-H, Yao C.-F. Tetrahedron 2013; 69: 3323
• 1f Shen Z, Lu X. Adv. Synth. Cat. 2009; 351: 3107
• 1g Kim JS, Han JH, Lee JJ, Jun YM, Lee BM, Kim BH. Tetrahedron Lett. 2008; 23: 3733
• 1h Yamane Y, Liu X, Hamasaki A, Ishida T, Haruta M, Yokoyama T, Tokunaga M. Org. Lett. 2009; 11: 5162
• 1i Fu W, Yang K, Chen J, Song Q. Org. Biomol. Chem. 2017; 15: 8354
• 1j Najahi E, Rakotoarivelo NV, Valentin A, Nepveu F. Eur. J. Med. Chem. 2014; 76: 369
• 2 Asao N, Sato K, Yamamoto Y. Tetrahedron Lett. 2003; 44: 5675
• 3 Gao G.-L, Niu Y.-N, Yan Z.-Y, Wang H.-L, Wang G.-W, Shaukat A, Liang Y.-M. J. Org. Chem. 2010; 75: 1305
• 4a Hu H, Yang F, Wu Y. J. Org. Chem. 2013; 78: 10506
• 4b Xu K, Sun S, Zhang G, Yang F, Wu Y. RSC Adv. 2014; 4: 32643
• 4c Liang Y, Xie Y.-X, Li J.-H. J. Org. Chem. 2006; 71: 379
• 4d Hachiya S, Asai K, Konishi G. Tetrahedron Lett. 2013; 54: 1839
• 4e Melzig L, Stemper J, Knochel P. Synthesis 2010; 2085
• 5 Garrett CE, Prasad K. Adv. Synth. Catal. 2004; 346: 889
• 6a DeRoy PL, Surprenant S, Bertrand-Laperle M, Yoakim C. Org. Lett. 2007; 9: 2741
• 6b Bujok R, Mąkosza M. Chem. Commun. 2016; 52: 12650
• 6c For a review on ONSH, see: Mąkosza M. Chem. Soc. Rev. 2010; 39: 2855
• 7a Ghosh AK, Zajc B. Org. Lett. 2006; 8: 1553
• 7b Mąkosza M, Bujok R. Synlett 2008; 586
• 7c Gueyrard D, Haddoub R, Salem A, Bacar NS, Goekjian PG. Synlett 2005; 520
• 7d For a review on the Smiles rearrangement, see: Holden CM, Greaney MF. Chem. Eur. J. 2017; 23: 8992
• 8 Pruger B, Hofmeister GE, Jacobsen CB, Alberg DG, Nielsen M, Jorgensen KA. Chem. Eur. J. 2010; 16: 3783
• 9a Pospíšil J, Sato H. J. Org. Chem. 2011; 76: 2269
• 9b Pospíšil J, Robiette R, Sato H, Debrus K. Org. Biomol. Chem. 2012; 10: 1225
• 10a Benischke AD, Leroux M, Knoll I, Knochel P. Org. Lett. 2016; 18: 3626
• 10b Arisawa M, Kuwajima M, Toriyama F, Li G, Yamaguchi M. Org. Lett. 2012; 14: 3804
• 11 Sun K, Sachwani R, Richert KJ, Driver TG. Org. Lett. 2009; 11: 3598
• 12 Rudenko AP, Vasilev AV. Russ. J. Org. Chem. 1995; 31: 1360
• 13 Melzig L, Metzger A, Knochel P. Chem. Eur. J. 2011; 17: 2948