PDF herunterladen
Synthesis 2022; 54(18): 4095-4103
DOI: 10.1055/a-1835-2188
paper

The Reaction of Ketoximes with Hypervalent Iodine Reagents: Beckmann Rearrangement and Hydrolysis to Ketones

Tomohiro Maegawa  ∗
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
,
Ryohei Oishi
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
,
Ayumi Maekawa
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
,
Kazutoshi Segi
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
,
Hiromi Hamamoto
b   Faculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku, Nagoya, 468-8502, Japan
,
Akira Nakamura 
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
c   Research Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu, Shiga, 525-8577, Japan
,
Yasuyoshi Miki∗
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
c   Research Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu, Shiga, 525-8577, Japan
› InstitutsangabenThis work was financially supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Numbers 19K16329 and 18K05132, and also supported by a 2021 Kindai University Research Enhancement Grant (KD2106).
› Weitere Informationen
    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

We investigated the reaction of ketoximes with hypervalent iodine reagents. A combination of PhI(OAc)2 and BF3·Et2O promoted the Beckmann rearrangement of ketoximes, thus yielding the corresponding amides. From a detailed investigation of the reaction, we determined that the Beckmann rearrangement is preceded by acetylation of the hydroxy group of the ketoxime in situ, accelerating the Beckmann rearrangement. We confirmed that the acetylated ketoxime undergoes the Beckmann rearrangement with BF3·Et2O. The reaction of ketoximes with Koser’s reagent [PhI(OH)OTs] in the presence of tetrahydrofuran results in hydrolysis, affording the corresponding ketones in high yields at room temperature.

Key words

ketoximes - hypervalent iodine reagents - Beckmann rearrangement - hydrolysis - amides - ketones

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1835-2188
  • Supporting Information


Publikationsverlauf

Eingereicht: 12. März 2022

Angenommen nach Revision: 26. April 2022

Accepted Manuscript online:
26. April 2022

Artikel online veröffentlicht:
08. Juni 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References

  • 1 Wuts PG. M. Greene’s Protective Groups in Organic Synthesis, 5th ed. John Wiley & Sons, Inc; Hoboken, NJ: 2014: 661
    CrossrefGoogle Scholar
    • 2a Craig D. The Beckmann and Related Reactions . In Comprehensive Organic Synthesis, Vol. 7. Trost BM, Fleming I. Pergamon Press; Oxford: 1991: 689-702
      CrossrefGoogle Scholar
    • 2b Gawley RE. Org. React. 1988; 35: 1
    • 3a Ghiaci M, Imanzadeh GH. Synth. Commun. 1998; 28: 2275
      Crossref
    • 3b Thomas B, Sugunan S. Microporous Mesoporous Mater. 2006; 96: 55
      Crossref
    • 3c Sugamoto K, Matsushita Y, Matsui T. Synth. Commun. 2011; 41: 879
      Crossref
    • 3d An N, Pi H, Liu L, Du W, Deng W. Chin. J. Chem. 2011; 29: 947
      Crossref

      For reviews see:
    • 4a Hypervalent Iodine Chemistry. Modern Developments in Organic Synthesis. In Topics in Current Chemistry, Vol. 224. Wirth T. Springer; Berlin: 2003
      Google Scholar
    • 4b Tohma H, Kita Y. Adv. Synth. Catal. 2004; 346: 111
    • 4c Moriarty RM. J. Org. Chem. 2005; 70: 2893
      CrossrefPubMed
    • 4d Wirth T. Angew. Chem. Int. Ed. 2005; 44: 3656
      CrossrefPubMed
    • 4e Zhdankin VV, Stang PJ. Chem. Rev. 2008; 108: 5299
      CrossrefPubMed
    • 4f Ochiai M. Synlett 2009; 159
    • 4g Dohi T, Kita Y. Chem. Commun. 2009; 2073
      CrossrefPubMed
    • 4h Duschek A, Kirsch SF. Angew. Chem. Int. Ed. 2011; 50: 1524
      CrossrefPubMed
    • 4i Merritt EA, Olofsson B. Synthesis 2011; 517
    • 4j Silva LF, Olofsson B. Nat. Prod. Rep. 2011; 28: 1722
    • 4k Yoshimura A, Zhdankin VV. Chem. Rev. 2016; 116: 3328
    • 4l Hypervalent Iodine Chemistry. In Topics in Current Chemistry, Vol. 373. Wirth T. Springer; Switzerland: 2016
      Google Scholar
  • 5 Nakamura A, Kanou H, Tanaka J, Imamiya A, Maegawa T, Miki Y. Org. Biomol. Chem. 2018; 16: 541
    CrossrefPubMed
  • 6 Oishi R, Segi K, Hamamoto H, Nakamura A, Maegawa T, Miki Y. Synlett 2018; 29: 1465
    Artikel in Thieme ConnectPubMed
    • 7a Hamamoto H, Umemoto H, Umemoto M, Ohta C, Doshita M, Miki Y. Synlett 2010; 2593
    • 7b Hamamoto H, Hattori S, Takemaru K, Miki Y. Synlett 2011; 1563
    • 7c Miki Y, Umemoto H, Doshita M, Hamamoto H. Tetrahedron Lett. 2012; 53: 1924
      Crossref
    • 7d Hamamoto H, Umemoto H, Umemoto M, Ohta C, Fujita E, Nakamura A, Maegawa T, Miki Y. Heterocycles 2015; 91: 561
      Crossref
    • 7e Nakamura A, Tanaka S, Imamiya A, Takane R, Ohta C, Fujimura K, Maegawa T, Miki Y. Org. Biomol. Chem. 2017; 15: 6702
      CrossrefPubMed
    • 7f Shibata A, Kitamoto S, Fujimura K, Hirose Y, Hamamoto H, Nakamura A, Miki Y, Maegawa T. Synlett 2018; 29: 2275
      Artikel in Thieme Connect
    • 7g Nakamura A, Takane R, Tanaka J, Morimoto J, Maegawa T. Heterocycles 2018; 97: 785
      Crossref
  • 8 Moriarty RM, Prakash O, Vavilikolanu PR. Synth. Commun. 1986; 16: 1247
    CrossrefPubMed
  • 9 Torisawa Y, Nishi T, Minamikawa J. Bioorg. Med. Chem. 2003; 11: 2205
    CrossrefPubMed
  • 10 Izquierdo S, Essafi S, Rosal I, Vidossich P, Pleixats R, Vallribera A, Ujaque G, Lledós A, Shafir A. J. Am. Chem. Soc. 2016; 138: 12747
    CrossrefPubMed
  • 11 Prakash GK. S, Moran MD, Mathew T, Olah GA. J. Fluorine Chem. 2009; 130: 806
    CrossrefPubMed
  • 12 Dooleweerdt K, Fors BP, Buchwald SL. Org. Lett. 2010; 12: 2350
    CrossrefPubMed
  • 13 Furuya Y, Ishihara K, Yamamoto H. J. Am. Chem. Soc. 2005; 127: 11240
    CrossrefPubMed
  • 14 Roy S, Gribble GW. Heterocycles 2006; 70: 51
    CrossrefPubMed
  • 15 Sakai N, Moriya T, Konohara T. J. Org. Chem. 2007; 72: 5920
    CrossrefPubMed
  • 16 Wang Y, Zhu D, Tang L, Wang S, Wang Z. Angew. Chem. Int. Ed. 2011; 50: 8917
    CrossrefPubMed
  • 17 Liu S, Yu Y, Liebeskind LS. Org. Lett. 2007; 9: 1947
    CrossrefPubMed
  • 18 Witosiñska A, Musielak B, Serda P, Owiñska M, Rys B. J. Org. Chem. 2012; 77: 9784
    CrossrefPubMed
  • 19 Huang K, Li S, Chang M, Zhang X. Org. Lett. 2013; 15: 484
    CrossrefPubMed
  • 20 Muthaiah S, Hong SH. Adv. Synth. Catal. 2012; 354: 3045
    CrossrefPubMed
  • 21 Moriyama K, Takemura M, Togo H. J. Org. Chem. 2014; 79: 6094
    CrossrefPubMed
  • 22 Chudinov YB, Gashev SB, Firgang SI, Semenov VV. Russ. Chem. Bull. 2007; 56: 1612
    Crossref
  • 23 Fernandes RA, Bethi V. RSC Adv. 2014; 4: 40561
    Crossref
  • 24 Ou-yang J, Zhang W, Qin F, Zuo Q, Xu S, Wang Y, Qin B, You S, Jia X. Org. Biomol. Chem. 2017; 15: 7374
    CrossrefPubMed