A Mild and Base-Free Synthesis of Unsymmetrical Diaryl Sulfones from Arylboronic Acids and Arylsulfonyl Hydrazides

Abstract

A mild and efficient synthesis of diaryl sulfones from arylboronic acids and arylsulfonyl hydrazides is described. Promoted by cupric acetate and in the absence of additional ligand and base, the cross-coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields at room temperature under neutral and ambient conditions.

Key words

diaryl sulfone - arylboronic acid - arylsulfonyl hydrazide - cross-coupling reaction - copper

• References and Notes

• 1a Williams TM, Ciccarone TM, MacTough SC, Rooney CS, Balani SK, Condra JK, Emini EA, Goldman ME, Greenlee WJ, Kauffman LR, O’Brien JA, Sardana VV, Schleif WA, Theoharides AD, Anderson PA. J. Med. Chem. 1993; 36: 1291
• 1b Artico M, Silvestri R, Massa S, Loi AG, Corrias S, Piras G, La Colla P. J. Med. Chem. 1996; 39: 522
• 1c Jones TR, Webber SE, Varney MD, Reddy MR, Lewis KK, Kathardekar V, Mazdiyasni H, Deal J, Nguyen D, Welsh KM, Webber S, Johnston A, Matthews DA, Smith WW, Janson CA, Bacquet RJ, Howland EF, Booth CL. J, Herrmann SM, Ward RW, White J, Bartlett CA, Morse CA. J. Med. Chem. 1997; 40: 677
• 1d Dinsmore CJ, Williams TM, O’Neill TJ, Liu D, Rands E, Culberson JC, Lobell RB, Koblan KS, Kohl NE, Gibbs JB, Oliff AI, Graham SL, Hartman GD. Bioorg. Med. Chem. Lett. 1999; 9: 3301
• 1e Sun ZY, Botros E, Su AD, Kim Y, Wang E, Baturay NZ, Kwon CH. J. Med. Chem. 2000; 43: 4160
• 1f Doherty GA, Kamenecka T, McCauley E, Van Riper G, Mumford RA, Tonga S, Hagmanna WK. Bioorg. Med. Chem. Lett. 2002; 12: 729
• 1g Pal M, Veeramaneni VR, Nagabelli M, Kalleda SR, Misra P, Casturib SR, Yeleswarapua KR. Bioorg. Med. Chem. Lett. 2003; 13: 1639
• 1h Otzen T, Wempe EG, Kunz B, Bartels R, Lehwark-Yvetot G, Hänsel W, Schaper KJ, Seydel JK. J. Med. Chem. 2004; 47: 240
• 1i Hartz RA, Arvanitis AG, Arnold C, Rescinito JP, Hung KL, Zhang G, Wong H, Langley DR, Gilligan PJ, Trainor GL. Bioorg. Med. Chem. Lett. 2006; 16: 934
• 2a Aldea R, Alper H. J. Org. Chem. 1995; 60: 8365
• 2b Reddy TI, Varma RS. Chem. Commun. 1997; 5: 471
• 2c Al-Maksoud W, Daniele S, Sorokin AB. Green Chem. 2008; 10: 447
• 2d Rahimizadeh M, Rajabzadeh G, Khatami SM, Eshghi H, Shiri A. J. Mol. Catal. A: Chem. 2010; 323: 59
• 2e Rostami A, Akradi J. Tetrahedron Lett. 2010; 51: 3501
• 3a Graybill BM. J. Org. Chem. 1967; 32: 2931
• 3b Ueda M, Uchiyama K, Kano T. Synthesis 1984; 323
• 3c Choudary BM, Chowdari NS, Kantam ML. J. Chem. Soc., Perkin Trans 2000; 1: 2689
• 3d Nara SJ, Harjani JR, Salunkhe MM. J. Org. Chem. 2001; 66: 8616
• 3e Frost CG, Hartley JP, Whittle AJ. Synlett 2001; 830
• 3f Bandgar BP, Kasture SP. Synth. Commun. 2001; 31: 1065
• 4a Suzuki H, Abe H. Tetrahedron Lett. 1995; 36: 6239
• 4b Baskin JM, Wang Z. Org. Lett. 2002; 4: 4423
• 4c Cacchi S, Fabrizi G, Goggiamani A, Parisi LM. Org. Lett. 2002; 4: 4719
• 4d Cacchi S, Fabrizi G, Goggiamani A, Parisi LM. Synlett 2003; 361
• 4e Cacchi S, Fabrizi G, Goggiamani A, Parisi LM, Bernini R. J. Org. Chem. 2004; 69: 5608
• 4f Bandgar BP, Bettigeri SV, Phopase J. Org. Lett. 2004; 13: 2105
• 4g Zhu W, Ma D. J. Org. Chem. 2005; 70: 2696
• 4h Kar A, Sayyed IA, Lo WF, Kaiser HM, Beller M, Tse MK. Org. Lett. 2007; 9: 3405
• 4i Huang F, Batey RA. Tetrahedron 2007; 63: 7667
• 4j Bian M, Xu F, Ma C. Synthesis 2007; 2951
• 4k Reeves DC, Rodriguez S, Heewon L, Haddad N, Krishnamurthy D, Senayake CH. Tetrahedron Lett. 2009; 50: 2870
• 5a Ballini R, Marcantoni E, Petrin M. Tetrahedron 1989; 45: 6791
• 5b Kamijo S, Al-Masum M, Yamamoto Y. Tetrahedron Lett. 1998; 39: 691
• 5c Taniguchi T, Idota A, Ishibashi H. Org. Biomol. Chem. 2011; 9: 3151
• 5d Li X, Xu X, Zhou C. Chem. Commun. 2012; 48: 12240
• 6a Liu B, Li J, Song FJ, You JS. Chem. Eur. J. 2012; 18: 10830
• 6b Yu XZ, Li XW, Wan BS. Org. Biomol. Chem. 2012; 10: 7479
• 6c Yang FL, Ma XT, Tian SK. Chem. Eur. J. 2012; 18: 1582
• 6d Yuen OY, So CM, Wong WT, Kwong FY. Synlett 2012; 23: 2714
• 7a Yang FL, Tian SK. Angew. Chem. Int. Ed. 2013; 125: 5029
• 7b Singh N, Singh R, Raghuvanshi DS, Singh KN. Org. Lett. 2013; 15: 5874
• 8 Beaulieu C, Guay D, Wang ZY, Evans DA. Tetrahedron Lett. 2004; 45: 3233
• 9 General Procedure Arylboronic acids (1.2 mmol), arylsulfonyl hydrazides (1.0 mmol), cupric acetate (1.5 mmol), and EtOH (2.0 mL) were taken in a 25 mL two-neck flask. The reaction mixture was stirred at r.t. for 6 h in air. The solution was evaporated under reduced pressure and H₂O (20 mL) was added, and then the mixture was extracted with EtOAc (4 10 mL). The extracts were combined and washed with brine (3 10 mL), dried over MgSO₄, filtered, evaporated, and purified by chromatog-raphy on silica gel to obtain the desired products with EtOAc–hexane (v/v = 1:5 to 1:10). The products were characterized by their spectral and analytical data and compared with those of the known compounds (see Supporting Information). Typical Data for Representative Compound: p-Ethyl-phenyl p-Tolyl Sulfone (Table 2, Entry 4) ¹H NMR (300 MHz, CDCl₃): δ = 7.85–7.81 (m, 4 H), 7.31–7.27 (m, 4 H), 2.68–2.66 (m, 2 H), 2.38 (s, 3 H), 1.22 (m, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 144.0, 139.1, 139.0, 129.9, 128.7, 127.6, 28.8, 21.6, 15.1. GC–MS (EI): m/z = 260 [M⁺]. Anal Calcd for C₁₅H₁₆O₂S C: 69.20; H, 6.19. Found: C, 69.12; H, 6.15.