Skip to main content
SpringerLink
Log in

Domino ring opening/cyclization of oxiranes for synthesis of functionalized 2H-pyran-5-carboxylate

  • Original Article
  • Published:
Molecular Diversity Aims and scope Submit manuscript

Abstract

A simple method for the synthesis of functionalized 2H-pyrans via a catalytic reaction of an oxirane, an alkyne, and a malonate has been developed in which a 6-exo-dig cyclization pathway is observed. In this transformation, the attack of in situ generated copper acetylides on oxiranes formed homopropargylic alcohol intermediates which further transferred to 2H-pyrans with the help of malonates.

Graphic abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Scheme 4

Similar content being viewed by others

References

  1. Kutateladze AG, Kuznetsov DM, Beloglazkina AA, Holt T (2018) Addressing the challenges of structure elucidation in natural products possessing the oxirane moiety. J Org Chem 83:8341–8352. https://doi.org/10.1021/acs.joc.8b01027

    Article  CAS  PubMed  Google Scholar 

  2. Das B, Reddy VS, Tehseen F, Krishnaiah M (2007) Catalyst-free highly regio- and stereoselective ring opening of epoxides and aziridines with sodium azide using poly(ethylene glycol) as an efficient reaction medium. Synthesis 2007:666–668. https://doi.org/10.1055/s-2007-965921

    Article  CAS  Google Scholar 

  3. Sabitha G, Babu RS, Rajkumar M, Yadav JS (2002) Cerium(III) chloride promoted highly regioselective ring opening of epoxides and aziridines using NaN3 in acetonitrile: a facile synthesis of 1,2-azidoalcohols and 1,2-azidoamines. Org Lett 4:343–345. https://doi.org/10.1021/ol016979q

    Article  CAS  PubMed  Google Scholar 

  4. Bhadra S, Adak L, Samanta S, Maidul Islam AKM, Mukherjee M, Ranu BC (2010) Alumina-supported Cu(II), a versatile and recyclable catalyst for regioselective ring opening of aziridines and epoxides and subsequent cyclization to functionalized 1,4-benzoxazines and 1,4-benzodioxanes. J Org Chem 75:8533–8541. https://doi.org/10.1021/jo101916e

    Article  CAS  PubMed  Google Scholar 

  5. Chen D, Shen G, Bao W (2009) An efficient cascade synthesis of various 2H-1,4-benzoxazin-3-(4H)-ones from o-halophenols and 2-halo-amides catalyzed by CuI. Org Biomol Chem 7:4067–4073. https://doi.org/10.1039/B906210F

    Article  CAS  PubMed  Google Scholar 

  6. Rao RK, Karthikeyan I, Sekar G (2012) Domino aziridine ring opening and Buchwald–Hartwig type coupling-cyclization by palladium catalyst. Tetrahedron 68:9090–9094. https://doi.org/10.1016/j.tet.2012.08.054

    Article  CAS  Google Scholar 

  7. Rao RK, Naidu AB, Sekar G (2009) Highly efficient copper-catalyzed domino ring opening and goldberg coupling cyclization for the synthesis of 3,4-dihydro-2H-1,4-benzoxazines. Org Lett 11:1923–1926. https://doi.org/10.1021/ol9003299

    Article  CAS  PubMed  Google Scholar 

  8. Jamieson C, Campbell RA, Cumming IA, Gillen KJ, Gillespie J, Kiczun M, Lamont Y, Lyons AJ, MacLean JKF, Moir EM, Morrow JA, Papakosta M, Rankovic Z, Smith L, Basten S, Kazemier B (2010) A novel series of positive modulators of the AMPA receptor: discovery and structure based hit-to-lead studies. Bioorg Med Chem Lett 20:5753–5756. https://doi.org/10.1016/j.bmcl.2010.07.138

    Article  CAS  PubMed  Google Scholar 

  9. Danilewicz JC, Abel SM, Brown AD, Fish PV, Hawkeswood E, Holland SJ, James K, McElroy AB, Overington J, Powling MJ, Rance DJ (2002) Design of selective thrombin inhibitors based on the (R)-Phe-Pro-Arg sequence. J Med Chem 45:2432–2453. https://doi.org/10.1021/jm011133d

    Article  CAS  PubMed  Google Scholar 

  10. Crawley GC, Dowell RI, Edwards PN, Foster SJ, McMillan RM, Walker ERH, Waterson D, Bird TGC, Bruneau P, Girodeau JM (1992) Methoxytetrahydropyrans. A new series of selective and orally potent 5-lipoxygenase inhibitors. J Med Chem 35:2600–2609. https://doi.org/10.1021/jm00092a010

    Article  CAS  PubMed  Google Scholar 

  11. Liang G, Sharum DT, Lam T, Totah NI (2013) 2-Methylenetetrahydropyrans: efficient partners in the carbonyl ene reaction. Org Lett 15:5974–5977. https://doi.org/10.1021/ol402843s

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Shin YJ, Yeom CE, Kim MJ, Kim BM (2008) A one-pot, solid-phase synthesis of secondary amines from reactive alkyl halides and an alkyl azide. Synlett 2008:89–93. https://doi.org/10.1021/ol402843s

    Article  CAS  Google Scholar 

  13. Schmidt B (2003) An olefin metathesis/double bond isomerization sequence catalyzed by an in situ generated ruthenium hydride species. Eur J Org Chem 2003:816–819. https://doi.org/10.1002/ejoc.200390124

    Article  Google Scholar 

  14. Fujino D, Yorimitsu H, Osuka A (2014) Regiocontrolled palladium-catalyzed arylative cyclizations of alkynols. J Am Chem Soc 136:6255–6258. https://doi.org/10.1021/ja5029028

    Article  CAS  PubMed  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Shahr-e-Qods Branch, Islamic Azad University, Tehran, Iran

    Alireza Varmazyar, Sajjad Sedaghat, Ahmad Nozad Goli-Kand & Samira Arab-Salmanabadi

  2. Material and Nuclear Fuel Cyclic Research School, NSTRI, Tehran, Iran

    Ahmad Nozad Goli-Kand

  3. Department of Chemistry, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran

    Mehdi Khalaj

Authors
  1. Alireza Varmazyar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sajjad Sedaghat
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ahmad Nozad Goli-Kand
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mehdi Khalaj
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Samira Arab-Salmanabadi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Sajjad Sedaghat or Mehdi Khalaj.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 5736 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Varmazyar, A., Sedaghat, S., Goli-Kand, A.N. et al. Domino ring opening/cyclization of oxiranes for synthesis of functionalized 2H-pyran-5-carboxylate. Mol Divers 24, 707–716 (2020). https://doi.org/10.1007/s11030-019-09978-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11030-019-09978-9

Keywords

Search

Navigation