Skip to content

Research at St Andrews

Polycyclic ethers and an unexpected dearomatisation reaction during studies towards the bioactive alkaloid, perophoramidine

Research output: Contribution to journalArticle

Author(s)

Craig A. Johnston, Ross P. Wilkie, Helmut Krauss, Andrew R. Neal, Alexandra M. Z. Slawin, Tomas Lebl, Nicholas J. Westwood

School/Research organisations

Abstract

The bioactive alkaloid natural product perophoramidine and the related family of compounds known as the communesins have inspired the synthesis community for more than a decade. Many of the elegant approaches have required the synthesis of complex intermediates that have not always reacted in the expected manner. In this study we describe a series of cyclic ether-containing precursors that were prepared during our synthetic studies towards these natural products. Attempts to open the cyclic ether ring and trap the resulting stabilised carbocation with a carbon nucleophile ultimately led to the preparation of a diallyl-substituted all carbon quaternary centre. Subsequent attempts to differentiate between the two allyl groups resulted in a relatively clean transformation to an unexpected compound. Extensive structural characterisation, including small molecule X-ray crystallography, showed that a dearomatisation reaction had occurred.
Close

Details

Original languageEnglish
Pages (from-to)3339-3347
JournalTetrahedron
Volume74
Issue number26
Early online date28 Apr 2018
DOIs
Publication statusPublished - 28 Jun 2018

    Research areas

  • Natural product, Ring opening reaction, Cyclic ether, Dearomatisation

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Synthesis of the natural product descurainolide and cyclic peptides from lignin-derived aromatics

    Ojo, O. S., Nardone, B., Musolino, S. F., Neal, A., Wilson, L., Lebl, T., Slawin, A. M. Z., Cordes, D. B., Taylor, J. E., Naismith, J. H., Smith, A. D. & Westwood, N. J., 14 Jan 2018, In : Organic & Biomolecular Chemistry. 16, 2, p. 266-273

    Research output: Contribution to journalArticle

  2. Use of bisulfite processing to generate high-β-O-4 content water-soluble lignosulfonates

    Miles-Barrett, D. M., Montgomery, J. R. D., Lancefield, C. S., Cordes, D. B., Slawin, A. M. Z., Lebl, T., Carr, R. & Westwood, N. J., 6 Feb 2017, In : ACS Sustainable Chemistry & Engineering . 5, 2, p. 1831-1839 9 p.

    Research output: Contribution to journalArticle

  3. The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins

    Miles-Barrett, D., Neal, A., Hand, C., Montgomery, J., Panovic, I., Ojo, O. S., Lancefield, C. S., Cordes, D. B., Slawin, A. M. Z., Lebl, T. & Westwood, N. J., 14 Nov 2016, In : Organic & Biomolecular Chemistry. 14, 42, p. 10023-10030 8 p.

    Research output: Contribution to journalArticle

  4. Total synthesis of dehaloperophoramidine using a highly diastereoselective Hosomi-Sakurai reaction

    Wilkie, R. P., Neal, A., Johnston, C. A., Voûte, N., Lancefield, C. S., Stell, M., Medda, F., Makiyi, E. F., Turner, E., Ojo, O. S., Slawin, A. M. Z., Lebl, T., Mullen, P., Harrison, D. J., Ireland, C. M. & Westwood, N. J., 14 Sep 2016, In : Chemical Communications. 52, 71, p. 10747-10750

    Research output: Contribution to journalArticle

Related by journal

  1. Tetrahedron (Journal)

    Stuart John Conway (Editor)
    2007 → …

    Activity: Publication peer-review and editorial work typesEditor of research journal

Related by journal

  1. Fluorine in pheromones: synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics

    Zhang, Q., Teschers, C. S., Callejo, R., Yang, M., Wang, M., Silk, P. J., Ryall, K., Roscoe, L. E., Cordes, D. B., Slawin, A. M. Z. & O'Hagan, D., 24 May 2019, In : Tetrahedron. 75, 21, p. 2917-2922

    Research output: Contribution to journalArticle

  2. Assessment of the regioselectivity in the condensation reaction of unsymmetrical o-phthaldialdehydes with alanine

    D'Hollander, A. C. A. & Westwood, N. J., 11 Jan 2018, In : Tetrahedron. 74, 2, p. 224-239

    Research output: Contribution to journalArticle

  3. Best practice considerations for using the selectivity factor, s, as a metric for the efficiency of kinetic resolutions

    Greenhalgh, M. D., Taylor, J. E. & Smith, A. D., 20 Sep 2018, In : Tetrahedron. 74, 38, p. 5554-5560 7 p.

    Research output: Contribution to journalArticle

  4. From one to two quaternary centers: ester or nitrile α-alkylation applied to bioactive alkaloids

    Voûte, N., Neal, A., Medda, F., Johnston, C. A., Slawin, A. M. Z. & Westwood, N. J., 8 Nov 2018, In : Tetrahedron. In press

    Research output: Contribution to journalArticle

  5. P-stereogenic wide bite angle diphosphine ligands

    Czauderna, C. F., Slawin, A. M. Z., Cordes, D. B., van der Vlugt, J. I. & Kamer, P. C. J., 14 Nov 2018, In : Tetrahedron. In press

    Research output: Contribution to journalArticle

ID: 252962799