Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2014; 25(12): 1739-1744
DOI: 10.1055/s-0033-1339117
DOI: 10.1055/s-0033-1339117
letter
Synthesis of Arylethyl (E)-Styrylsulfones and Arylsulfones by One-Pot DIBAL-H/NaH-Mediated Reaction of β-Ketosulfones
Further Information
Publication History
Received: 25 March 2014
Accepted: 18 April 2014
Publication Date:
02 June 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201412/lookinside/thumbnails/10.1055-s-0033-1339117-1.jpg)
Abstract
A facile one-pot synthetic route for preparing a series of arylethyl (E)-styrylsulfones or arylethyl arylsulfones is developed. The efficient one-pot DIBAL-H/NaH-mediated route includes reduction of α-benzyl-β-arylketosulfones and retroaldol/aldol or retroaldol reaction of the resulting intermediate. The DIBAL-H/NaH-mediated reaction mechanism has been discussed.
-
References and Notes
- 1a Simpkins NS In Sulfones in Organic Synthesis. Baldwin JE. Pergamon Press; Oxford: 1993
- 1b Trost BM. Comprehensive Organic Chemistry . Pergamon Press; Oxford: 1991
- 1c El-Awa A, Noshi MN, Mollat du Jourdin X, Fuchs PL. Chem. Rev. 2009; 109: 2315
- 1d Trost BM. Bull. Chem. Soc. Jpn. 1988; 61: 107
- 1e The Chemistry of Sulphones and Sulphoxides . Patai S, Rappoport Z, Stirling C. Wiley; Chichester: 1988
- 2a Pospisil J, Sato H. J. Org. Chem. 2011; 76: 2269
- 2b Sreedhar B, Rawat VS. Synlett 2012; 23: 413
- 2c Kumar A, Muthyala MK. Tetrahedron Lett. 2011; 52: 5368
- 2d Suryakiran N, Reddy TS, Ashalatha K, Lakshman M, Venkateswarlu Y. Tetrahedron Lett. 2006; 47: 3853
- 2e Lu Q, Zhang J, Zhao G, Qi Y, Wang H, Lei W. J. Am. Chem. Soc. 2013; 135: 11481
- 2f Tsui GC, Glenadel Q, Lau C, Lautens M. Org. Lett. 2011; 13: 208
- 2g Curti C, Laget M, Carle AO, Gellis A, Vanelle P. Eur. J. Med. Chem. 2007; 42: 880
- 2h Bin JK, Lee JS, Kim K. Org. Lett. 2004; 6: 4297
- 3a Reddy DB, Reddy NS, Reddy MV. R, Balasubramanyam S. Org. Prep. Proced. Int. 1998; 20: 205
- 3b Kabalka GW, Guchhait SK. Tetrahedron Lett. 2004; 45: 4021
- 3c Nishimura T, Takiguchi Y, Hayashi T. J. Am. Chem. Soc. 2012; 134: 9086
- 3d Gotor V, Rebolledo F, Liz R. Tetrahedron: Asymmetry 2001; 12: 513
- 3e Wan X, Meng Q, Zhang H, Sun Y, Fan W, Zhang Z. Org. Lett. 2007; 9: 5613
- 3f Suryakiran N, Reddy TS, Suresh V, Lakshman M, Venkateswarlu Y. Tetrahedron Lett. 2006; 47: 4319
- 3g Suryakiran N, Prabhakar P, Reddy TS, Mahesh KC, Rajesh K, Venkateswarlu Y. Tetrahedron Lett. 2007; 48: 877
- 3h Ni C, Zhang L, Hu J. J. Org. Chem. 2009; 74: 3767
- 3i Marco J.-L, Fernandez I, Khiar N, Fernandez P, Romero A. J. Org. Chem. 1995; 60: 6678
- 3j Kumar D, Sundaree MS, Patel G, Rao VS, Varma RS. Tetrahedron Lett. 2006; 47: 8239
- 3k Curti C, Crozet MD, Vanelle P. Tetrahedron 2009; 65: 200
- 4a Reddy MV. R, Mallireddigari MR, Cosenza SC, Pallela VR, Iqbal NM, Robell KA, Kang AD, Reddy EP. J. Med. Chem. 2008; 51: 86
- 4b Reddy MV. R, Venkatapuram P, Mallireddigari MR, Pallela VR, Cosenza SC, Robell KA, Akula B, Hoffman BS, Reddy EP. J. Med. Chem. 2011; 54: 6254
- 4c Vedula MS, Pulipaka AB, Venna C, Chintakuta VK, Jinnapally S, Kattuboina VA, Vallakati V, Akella V, Rajgopal S, Reka AK, Teepireddy SK, Mammoor PK, Rajagopalan R, Bulusu G, Khandelwal A, Upreti VV, Mamidi SR. Eur. J. Med. Chem. 2003; 38: 811
- 4d Adler V, Franklin CC, Kraft AS. Proc. Natl. Acad. Sci. U.S.A. 1992; 89: 5341
- 4e Lu M, Merali S, Gordon R, Jiang J, Li Y, Mandeli J, Duan X, Fallon J, Holland JF. Genes Cancer 2011; 2: 985
- 4f Gumireddy K, Reddy MV. R, Cosenza SC, Nathan RB, Baker SJ, Papathi N, Jiang J, Holland J, Reddy EP. Cancer Lett. 2005; 7: 275
- 4g Reddy EP, Reddy MV. R. US 6359013 B1, 2002
- 5a Ashcroft CP, Hellier P, Pettman A, Wakinson S. Org. Process Res. Dev. 2011; 15: 98
- 5b Madasu SB, Vekariya NA, Hari Kiran MN. V. D, Gupta B, Islam A, Douglas PS, Babu KR. Beilstein J. Org. Chem. 2012; 8: 1400
- 6a Padwa A, Kline DN, Murphree SS, Yeske PE. J. Org. Chem. 1992; 57: 298
- 6b Padwa A, Kline DN, Noman BH. Tetrahedron Lett. 1988; 29: 265
- 6c Padwa A, Yeske PE. J. Am. Chem. Soc. 1988; 110: 1617
- 6d Padwa A, Murphree SS, Yeske PE. Tetrahedron Lett. 1990; 31: 2983
- 6e Wu Z, Shen R, Ren L, Huang X. Synthesis 2005; 2171
- 7a Kazmaier U, Wesquet A. Synlett 2005; 1271
- 7b VanZanten A, Mullaugh K, Harrington R, Kiefer A, Carlson D, Mastarone D, Lipchik C, Murphree SS. Synthesis 2004; 2611
- 7c Xu L, Cheng J, Trudell ML. J. Org. Chem. 2003; 68: 5388
- 7d Achard T, Lepronier A, Clavier H, Giordano L, Tenaglia A, Buono G, Gimbert Y. Angew. Chem. Int. Ed. 2011; 50: 3552
- 7e Harvey IW, Phillips ED, Whitman GH, Hueso-Rodriguez JA, Elson SW. Tetrahedron 1997; 53: 6493
-
7f Harmata M, Kahraman M, Adenu G, Barnes CL. Heterocycles 2004; 62: 583
- 7g Denmark SE, Harmata MA, White KS. J. Org. Chem. 1987; 52: 4031
- 8a Cacchi S, Fabrizi G, Goggiamani A, Panrisi LM. Org. Lett. 2002; 4: 4719
- 8b Cacchi S, Fabrizi G, Goggiamani A, Panrisi LM. Synlett 2003; 361
- 8c Cacchi S, Fabrizi G, Goggiamani A, Panrisi LM. Berning R. J. Org. Chem. 2004; 69: 5608
- 8d Bandgar BP, Bettigeri SV, Phopase J. Org. Lett. 2004; 6: 2105
- 8e Baskin JM, Wang ZY. Org. Lett. 2002; 4: 4423
- 8f Feng XW, Wang J, Zhang J, Yang J, Wang N, Yu X. Q. Org. Lett. 2010; 12: 4408
- 8g Kar A, Sayyed IA, Lo WF, Kaiser HM, Beller M, Tse MK. Org. Lett. 2007; 9: 3405
- 8h Zhu W, Ma D. J. Org. Chem. 2005; 70: 2696
- 8i Redddy M, Reddy P, Sreedhar B. Adv. Synth. Catal. 2010; 352: 1861
- 8j Ueda M, Hartwig JF. Org. Lett. 2010; 12: 92
- 9a Rocke B, Bahnck KB, Herr M, Lavergne S, Mascitti V, Perreault C, Polivkova J, Shavnya A. Org. Lett. 2014; 16: 154
- 9b Deeming AS, Russell CJ, Hennessy AJ, Willis MC. Org. Lett. 2014; 16: 150
- 9c Umierski N, Manolikakes G. Org. Lett. 2013; 15: 4972
- 10a Umierski N, Manolikakes G. Org. Lett. 2013; 15: 188
- 10b Qin Q, Mague JT, Pascal RA. Org. Lett. 2010; 12: 928
- 10c Maloney K, Kuethe J, Linn K. Org. Lett. 2011; 13: 102
- 10d Li Y, Cheng K, Lu X, Sun J. Adv. Synth. Catal. 2010; 352: 1876
- 11 CCDC 979312 (5a), 982010 (5r), and 979313 (6k) contain the supplementary crystallographic data for this paper. This data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].
- 12 Representative Procedure for the Synthesis of Skeleton 5DIBAL-H (1.0 M in hexane, 0.5 mL, 0.5 mmol) was added to a solution of substituted β-ketosulfones 3 (0.5 mmol) in THF (10 mL) at r.t. The reaction mixture was stirred at r.t. for 10 min. NaH (60% in oil, 60 mg, 1.5 mmol) was added to the stirred solution at r.t. The reaction mixture was stirred at r.t. for 8 h. NH4Cl aq (15%, 1 mL) was added to the reaction mixture, and the solvent was concentrated. The residue was diluted with H2O (10 mL), and the mixture was extracted with CH2Cl2 (3 × 20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford the crude product. Purification on silica gel (hexanes–EtOAc = 10:1 to 6:1) afforded skeleton 5.Compound 5a: yield 84% (114 mg); colorless solid; mp 63–65 °C (recrystallized from hexanes and EtOAc). ESI-HRMS: m/z calcd for C16H17O2S [M+ + 1]: 273.0949; found: 273.0952. 1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 15.6 Hz, 1 H), 7.48–7.39 (m, 5 H), 7.33–7.21 (m, 5 H), 6.72 (d, J = 15.2 Hz, 1 H), 3.39–3.35 (m, 2 H), 3.18–3.14 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 144.97, 137.52, 132.12, 131.36, 129.08 (2×), 128.85 (2×), 128.55 (2×), 128.40 (2×), 126.95, 124.68, 56.50, 28.78. Anal. Calcd for C16H16O2S: C, 70.56; H, 5.92. Found: C, 70.75; H, 6.30. Single-crystal X-ray crystallography: crystal of compound 5a was grown by slow diffusion of EtOAc into a solution of compound 5a in CH2Cl2 to yield colorless prisms. The compound crystallizes in the orthorhombic crystal system, space group Pna21, a = 26.9302(15) Å, b = 9.6456(5) Å, c = 5.2760(5) Å, V = 1372.01(17) Å3, Z = 4, δ calcd = 1.318 g cm–3, F(000) = 576, 2θ range 1.511–25.057°, R indices (all data) R1 = 0.0419, wR2 = 0.1113.
For recent synthesis of β-ketosulfones, see:
For vinyl sulfones, see:
For β-hydroxysulfones, see:
For β-halosulfones, see:
For other sulfonyl derivatives, see:
For biological activities of styryl sulfones, see:
For metal-mediated synthesis of disubstituted sulfones for Pd, see:
For Cu, see:
For Fe, see:
For Ir, see:
For very recent examples for the synthesis of disubstituted sulfones from halides and sulfinates that were prepared in situ from organomatals and SO2, see for Zn:
For Mg, see:
For Li, see:
For recent metal-free synthetic examples, see: