Download PDF
Synlett 2018; 29(03): 340-343
DOI: 10.1055/s-0036-1591496
letter
© Georg Thieme Verlag Stuttgart · New York

Aluminum(III) Chloride Promoted Oxygen Transfer: Selective Oxidation of Sulfides to Sulfoxides

Yongtao Xie
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Yuxin Li
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Sha Zhou
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Shaa Zhou
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Yan Zhang
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Minggui Chen
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
,
Zhengming Li*
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Weijin Road 94th, Tianjin 300071, P. R. of China   Email: zml@nankal.edu.cn
› Author AffiliationsWe acknowledge financial support from the Natural Science Foundation of China (NSFC, Grant Nos. 31370039 and 21602118) and from the Tianjin Natural Science Foundation (16JCYBJC29400).
Further Information

Publication History

Received: 10 August 2017

Accepted after revision: 26 September 2017

Publication Date:
24 November 2017 (online)

    Permissions and Reprints All articles of this category


Abstract

An efficient selective oxidation of sulfides to sulfoxides has been developed by means of AlCl3-promoted oxygen transfer from phenyliodine diacetate [PhI(OAc)2]. AlCl3 proved to be the optimal ­Lewis acid for the activation of PhI(OAc)2. Various substituted sulfides were selectively transformed into the corresponding sulfoxides in good to excellent yields (≤99%). The high efficiency, excellent functional-group compatibility, broad substrate scope, and mild conditions render the current transformation useful for the synthesis of sulfoxides.

Key words

aluminum trichloride - oxygen transfer - oxidation - sulfides - sulfoxides

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591496.
  • Supporting Information
 

  • References and Notes

    • 1a Carreno MC. Chem. Rev. 1995; 95: 1717
      Crossref
    • 1b Oyama T. Naka K. Chujo Y. Macromolecules 1999; 32: 5240
      Crossref
    • 1c Legros J. Dehli JR. Bolm C. Adv. Synth. Catal. 2005; 347: 19
      Crossref
    • 1d Bentley R. Chem. Soc. Rev. 2005; 34: 609
      CrossrefPubMed
    • 1e Numata M. Aoyagi Y. Tsuda Y. Yarita T. Takatsu A. Anal. Chem. 2007; 79: 9211
      CrossrefPubMed
    • 1f Dini I. Tenore GC. Dini A. J. Nat. Prod. 2008; 71: 2036
      CrossrefPubMed
    • 1g El-Aasr M. Fujiwara Y. Takeya M. Ikeda T. Tsukamoto S. Ono M. Nakano D. Okawa M. Kinjo J. Yoshimitsu H. Nohara T. J. Nat. Prod. 2010; 73: 1306
      CrossrefPubMed
    • 1h Wyche TP. Piotrowski JS. Hou Y. Braun D. Deshpande R. McIlwain S. Ong IM. Myers CL. Guzei IA. Westler WM. Andes DR. Bugni TS. Angew. Chem. Int. Ed. 2014; 53: 11583
      CrossrefPubMed
    • 2a Fernández I. Khiar N. Chem. Rev. 2003; 103: 3651
      CrossrefPubMed
    • 2b Lang F. Li D. Chen J. Chen J. Li L. Cun L. Zhu J. Deng J. Liao J. Adv. Synth. Catal. 2010; 352: 843
      Crossref
    • 2c Chen J. Chen J. Lang F. Zhang X. Cun L. Zhu J. Deng J. Liao J. J. Am. Chem. Soc. 2010; 132: 4552
      CrossrefPubMed
    • 2d Jin S.-S. Wang H. Xu M.-H. Chem. Commun. 2011; 47: 7230
      CrossrefPubMed
    • 2e Qi W.-Y. Zhu T.-S. Xu M.-H. Org. Lett. 2011; 13: 3410
      CrossrefPubMed
    • 2f Chen C. Gui J. Li L. Liao J. Angew. Chem. Int. Ed. 2011; 50: 7681
      CrossrefPubMed
    • 2g Du L. Cao P. Xing J. Lou Y. Jiang L. Li L. Liao J. Angew. Chem. Int. Ed. 2013; 52: 4207
      CrossrefPubMed
    • 2h Wang D. Cao P. Wang B. Jia T. Lou Y. Wang M. Liao J. Org. Lett. 2015; 17: 2420
      CrossrefPubMed
    • 2i Barrett MJ. Khan GF. Davies PW. Grainger RS. Chem. Commun. 2017; 53: 5733
      CrossrefPubMed
    • 2j Otocka S. Kwiatkowska M. Madalińska L. Kiełbasiński P. Chem. Rev. 2017; 117: 4147
      CrossrefPubMed
    • 3a Omura K. Swern D. Tetrahedron 1978; 34: 1651
      Crossref
    • 3b Khenkin AM. Neumann R. J. Am. Chem. Soc. 2002; 124: 4198
      CrossrefPubMed
    • 4a Fernández de la Pradilla R. Colomer I. Viso A. Org. Lett. 2012; 14: 3068
      CrossrefPubMed
    • 4b Colomer I. Gheewala C. Simal C. Velado M. Fernández de la Pradilla R. Viso A. J. Org. Chem. 2016; 81: 4081
      CrossrefPubMed
    • 5a Eberhart AJ. Cicoira C. Procter DJ. Org. Lett. 2013; 15: 3994
      CrossrefPubMed
    • 5b Eberhart AJ. Procter DJ. Angew. Chem. Int. Ed. 2013; 52: 4008
      CrossrefPubMed
    • 5c Eberhart AJ. Shrives H. Zhang Y. Carrër A. Parry AV. S. Tate DJ. Turner ML. Procter DJ. Chem. Sci. 2016; 7: 1281
      CrossrefPubMed
    • 5d Fernández-Salas JA. Eberhart AJ. Procter DJ. J. Am. Chem. Soc. 2016; 138: 790
      CrossrefPubMed
    • 5e Yanagi T. Otsuka S. Kasuga Y. Fujimoto K. Murakami K. Nogi K. Yorimitsu H. Osuka A. J. Am. Chem. Soc. 2016; 138: 14582
      CrossrefPubMed
    • 5f Zhang Q. Wang W. Gao C. Cai R.-R. Xu R.-S. RSC Adv. 2017; 7: 20123
      Crossref
    • 6a Chinnusamy T. Reiser O. ChemSusChem 2010; 3: 1040
      CrossrefPubMed
    • 6b Neveselý T. Svobodová E. Chudoba J. Sikorski M. Cibulka R. Adv. Synth. Catal. 2016; 358: 1654
      Crossref
    • 7a Legros J. Bolm C. Angew. Chem. Int. Ed. 2003; 42: 5487
      CrossrefPubMed
    • 7b Legros J. Bolm C. Angew. Chem. Int. Ed. 2004; 43: 4225
      CrossrefPubMed
    • 7c Griffin RJ. Henderson A. Curtin NJ. Echalier A. Endicott JA. Hardcastle IR. Newell DR. Noble ME. M. Wang L.-Z. Golding BT. J. Am. Chem. Soc. 2006; 128: 6012
      CrossrefPubMed
    • 7d Egami H. Katsuki T. J. Am. Chem. Soc. 2007; 129: 8940
      CrossrefPubMed
    • 7e Li B. Liu A.-H. He L.-N. Yang Z.-Z. Gao J. Chen K.-H. Green Chem. 2012; 14: 130
      Crossref
    • 7f Gan S. Yin J. Yao Y. Liu Y. Chang D. Zhua D. Shi L. Org. Biomol. Chem. 2017; 15: 2647
      CrossrefPubMed
    • 7g Voutyritsa E. Triandafillidi I. Kokotos CG. Synthesis 2017; 49: 917
      Article in Thieme Connect
  • 8 Moorthy JN. Senapati K. Parida KN. Jhulki S. Sooraj K. Nair NN. J. Org. Chem. 2011; 76: 9593
    CrossrefPubMed
    • 9a Zhang H. Chen C.-Y. Liu R.-H. Xu Q. Liu J.-H. Synth. Commun. 2008; 38: 4445
      Crossref
    • 9b Kinen CO. Rossi LI. de Rossi RH. J. Org. Chem. 2009; 74: 7132
      CrossrefPubMed
    • 9c Maleki B. Hemmati S. Sedrpoushan A. Ashrafia SS. Veisi H. RSC Adv. 2014; 4: 40505
      Crossref
    • 9d Hu Y. Fang D. Xing R. RSC Adv. 2014; 4: 51140
      Crossref
    • 9e Baig N. Madduluri VK. Sah AK. RSC Adv. 2016; 6: 28015
      Crossref
    • 9f Yu B. Diao Z.-F. Liu A.-H. Han X. Li B. He L.-N. Liu X.-M. Curr. Org. Synth. 2014; 11: 156
      Crossref
  • 10 Yoshimura A. Zhdankin VV. Chem. Rev. 2016; 116: 3328
    CrossrefPubMed
    • 12a Yusubov MS. Yusubova RY. Funk TV. Chi K.-W. Zhdankin VV. Synthesis 2009; 2505
      Article in Thieme Connect
    • 12b Yu B. Guo C.-X. Zhong C.-L. Diao Z.-F. He L.-N. Tetrahedron Lett. 2014; 55: 1818
      Crossref
  • 13 Xie Y. Zhou B. Zhou S. Zhou S. Wei W. Liu J. Zhan Y. Cheng D. Chen M. Li Y. Wang B. Xue X.-S. Li Z. ChemistrySelect 2017; 2: 1620
    Crossref
  • 14 Izquierdo S. Essafi S. del Rosal I. Vidossich P. Pleixats R. Vallribera A. Ujaque G. Lledós A. Shafir A. J. Am. Chem. Soc. 2016; 138: 12747
    CrossrefPubMed
  • 15 The composition of the byproduct mixture was rather complicated. The main byproduct, (phenylsulfanyl)methyl acetate was isolated in 37% yield.
  • 16 Sulfoxides 2; General Procedure A 25 mL glass tube was charged with the appropriate sulfide 1 (1 mmol), MeOH (0.5 mL), and CH2Cl2 (4.5 mL). AlCl3 (0.5 mmol) was added, and the mixture was stirred at r.t. for 1 min. PhI(OAc)2 (1.0 equiv) was then added and the solution was stirred at r.t. until the sulfide was consumed (TLC). The solvent was removed under reduced pressure and the crude product was purified by column chromatography [silica gel (200–300 mesh), EtOAc–PE]. Methyl Phenyl Sulfoxide (2a) Colorless oil; yield: 138.6 mg (99%). 1H NMR (400 MHz, CDCl3): δ = 7.65 (dd, J = 7.8, 1.8 Hz, 2 H), 7.56–7.47 (m, 3 H), 2.72 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 145.33, 130.99, 129.28, 123.41, 43.71. MS (ESI): m/z [M + H]+ calcd for C7H9OS: 141.0; found: 141.0. 4-Fluorophenyl Methyl Sulfoxide (2b) Colorless oil; yield: 132.7 mg (84%). 1H NMR (400 MHz, CDCl3): δ = 7.70–7.63 (m, 2 H), 7.28–7.21 (m, 2 H), 2.73 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 165.47, 162.97, 140.94, 125.88, 125.80, 116.73, 116.50, 43.97. MS (ESI): m/z [M + H]+ calcd for C7H8FOS: 159.0; found: 158.8. 4-Chlorophenyl Methyl Sulfoxide (2c) Colorless oil; yield: 160.1 mg (92%). 1H NMR (400 MHz, CDCl3): δ = 7.59 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.6 Hz, 2 H), 2.72 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 144.05, 137.06, 129.52, 124.92, 43.84. MS (ESI): m/z [M + H]+ calcd for C7H8ClOS: 175.0; found: 175.1. 4-Bromophenyl Methyl Sulfoxide (2d) White solid; yield: 189.7 mg (87%); mp 79–81°C. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 8.5 Hz, 2 H), 7.51 (d, J = 8.5 Hz, 2 H), 2.70 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 144.85, 132.58, 125.47, 125.19, 44.00. MS (ESI): m/z [M + H]+ calcd for C7H8BrOS: 218.9; found: 218.9.