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Synthesis 2022; 54(22): 5128-5138
DOI: 10.1055/s-0037-1610790
paper

A General Way to Spiro-Annulated 2-Benzoxepines via Rh2(esp)2-Catalyzed [5+2] Cycloaddition of Diazo Arylidene Succinimides to Ketones

Anastasia Vepreva
a   Saint Petersburg State University, Petersburg, 199034, Russian Federation
,
Grigory Kantin
a   Saint Petersburg State University, Petersburg, 199034, Russian Federation
,
Mikhail Krasavin  ∗
a   Saint Petersburg State University, Petersburg, 199034, Russian Federation
b   Immanuel Kant Baltic Federal University, Kaliningrad 236041, Russian Federation
,
Dmitry Dar’in  ∗
a   Saint Petersburg State University, Petersburg, 199034, Russian Federation
› Author AffiliationsThis research was supported by the Russian Foundation for Basic Research (project grant 21-53-12001).
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Abstract

The formation of spirocyclic 2-benzoxepines by Rh2(esp)2-catalyzed decomposition of diazo arylidene succinimides in the presence of ketones was investigated. This transformation, which is a formal [5+2] cycloaddition of styryl rhodium carbenes to the carbonyl group, occurs in high yields under mild conditions, with high carbonyl substrate tolerance and diastereoselectivity. The developed general method opens access to rare spiro (hetero)cyclic scaffolds with great potential in drug discovery.

Key words

spirocyclic scaffold - 2-benzoxepines - cyclic α-diazocarbonyl compounds - conjugated carbonyl ylide - electrocyclization

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610790.
  • Supporting Information


Publication History

Received: 11 November 2021

Accepted after revision: 08 December 2021

Article published online:
26 January 2022

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  • References

  • 1 Chupakhin E, Babich O, Prosekov A, Asyakina L, Krasavin M. Molecules 2019; 24: 4165
    CrossrefPubMed
  • 2 Hiesinger K, Dar’in D, Proschak E, Krasavin M. J. Med. Chem. 2021; 64: 150
    CrossrefPubMed
  • 3 Zheng Y, Tice CM, Singh SB. Bioorg. Med. Chem. Lett. 2014; 24: 3673
    CrossrefPubMed
  • 4 Solovyev I, Eremeyeva M, Zhukovsky D, Dar’in D, Krasavin M. Tetrahedron Lett. 2021; 62: 152671
    Crossref
  • 5 Dar’in D, Kantin G, Bakulina O, Inyutina A, Chupakhin E, Krasavin M. J. Org. Chem. 2020; 85: 15586
    CrossrefPubMed
  • 6 Laha D, Bhat RG. Asian J. Org. Chem. 2020; 9: 918
    Crossref
  • 7 Inyutina A, Dar’in D, Kantin G, Krasavin M. Org. Biomol. Chem. 2021; 19: 5068
    CrossrefPubMed
  • 8 Inyutina A, Kantin G, Dar’in D, Krasavin M. J. Org. Chem. 2021; 86: 13673
    CrossrefPubMed
  • 10 Butkevich AN, Corbu A, Meerpoel L, Stansfield I, Angibaud P, Bonnet P, Cossy J. Org. Lett. 2012; 14: 4998
    CrossrefPubMed
    • 11a Maier CA, Wünsch B. Eur. J. Org. Chem. 2003; 714
      Crossref
    • 11b Maestrup EG, Wiese C, Schepmann D, Brust P, Wünsch B. Bioorg. Med. Chem. 2011; 19: 393
      CrossrefPubMed
  • 12 Bohme H, Hitzel V. Arch. Pharm. 1974; 306: 948
    CrossrefPubMed
  • 13 Boerth JA, Hummel JR, Ellman JA. Angew. Chem. Int. Ed. 2016; 55: 1
    CrossrefPubMed
  • 14 Hamaguchi M, Takahashi K, Oshima T, Tamura H. Tetrahedron Lett. 2003; 44: 4339
    Crossref
    • 15a Chupakhin EG, Kantin GP, Dar’in DV, Krasavin M. Mendeleev Commun. 2021; 31: 36
      Crossref
    • 15b Chupakhin E, Gecht M, Ivanov A, Kantin G, Dar’in D, Krasavin M. Synthesis 2021; 53: 1292
      Article in Thieme Connect