Skip to content

Research at St Andrews

Tandem palladium and isothiourea relay catalysis: enantioselective synthesis of α-amino acid derivatives via allylic amination and [2,3]-sigmatropic rearrangement

Research output: Research - peer-reviewArticle

DOI

Open Access permissions

Open

Author(s)

Stephanie S. M. Spoehrle, Thomas H. West, James E. Taylor, Alexandra M. Z. Slawin, Andrew D. Smith

School/Research organisations

Abstract

A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-α-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.
Close

Details

Original languageEnglish
Pages (from-to)11895-11902
JournalJournal of the American Chemical Society
Volume139
Issue number34
Early online date1 Aug 2017
DOIs
StatePublished - 30 Aug 2017

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

View graph of relations

Related by author

  1. A C=O•••isothiouronium interaction dictates enantiodiscrimination in acylative kinetic resolution of tertiary heterocyclic alcohols

    Greenhalgh, M. D., Smith, S. M., Walden, D. M., Taylor, J. E., Brice, Z., Robinson, E. R. T., Fallan, C., Cordes, D. B., Slawin, A. M. Z., Richardson, H. C., Grove, M. A., Cheong, P. H-Y. & Smith, A. D. 12 Mar 2018 In : Angewandte Chemie International Edition. 57, 12, p. 3200-3206

    Research output: Research - peer-reviewArticle

  2. 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: Research - peer-reviewArticle

  3. Enantioselective stereodivergent nucleophile-dependent isothiourea-catalysed domino reactions

    Matviitsuk, A., Taylor, J. E., Cordes, D. B., Slawin, A. M. Z. & Smith, A. D. 5 Dec 2016 In : Chemistry - A European Journal. 22, 49, p. 17748-17757 10 p.

    Research output: Research - peer-reviewArticle

  4. Isothiourea-catalysed enantioselective pyrrolizine synthesis: synthetic and computational studies

    Stark, D. G., Williamson, P., Gayner, E. R., Musolino, S. F., Kerr, R. W. F., Taylor, J. E., Slawin, A. M. Z., O'Riordan, T. J. C., Macgregor, S. A. & Smith, A. D. 14 Oct 2016 In : Organic & Biomolecular Chemistry. 14, 38, p. 8957-8965 9 p.

    Research output: Research - peer-reviewArticle

  5. Organocatalytic Synthesis of Fused Bicyclic 2,3-Dihydro-1,3,4-oxadiazoles through an Intramolecular Cascade Cyclization

    Fugard, A. J., Thompson, B. K., Slawin, A. M. Z., Taylor, J. E. & Smith, A. D. 4 Dec 2015 In : Organic Letters. 17, 23, p. 5824-5827 4 p.

    Research output: Research - peer-reviewArticle

Related by journal

  1. An environmentally-responsive reciprocal replicating network

    Robertson, C. C., Mackenzie, H. W., Kosikova, T. & Philp, D. 6 Jun 2018 In : Journal of the American Chemical Society. 140, 22, p. 6832-6841 10 p.

    Research output: Research - peer-reviewArticle

  2. Distance measurement of a non-covalently bound Y@C82 Pair with double electron electron resonance spectroscopy

    Gil-Ramírez, G., Shah, A., El Mkami, H., Porfyrakis, K., Briggs, A. D., Morton, J. J. L., Anderson, H. L. & Lovett, J. E. 6 Jun 2018 (Accepted/In press) In : Journal of the American Chemical Society. Just Accepted

    Research output: Research - peer-reviewArticle

  3. A structural model of a P450-ferredoxin complex from orientation-selective double electron-electron resonance spectroscopy

    Bowen, A. M., Johnson, E. O. D., Mercuri, F., Hoskins, N. J., Qiao, R., McCullagh, J. S. O., Lovett, J. E., Bell, S. G., Zhou, W., Timmel, C. R., Wong, L. L. & Harmer, J. R. 21 Feb 2018 In : Journal of the American Chemical Society. 140, 7, p. 2514-2527

    Research output: Research - peer-reviewArticle

  4. Interrogating Pd(II) anion metathesis using a bifunctional chemical probe

    Molloy, J. J., Seath, C. P., West, M. J., McLaughlin, C., Fazakerley, N. J., Kennedy, A. R., Nelson, D. J. & Watson, A. J. B. 10 Jan 2018 In : Journal of the American Chemical Society. 140, 1, p. 126-130

    Research output: Research - peer-reviewArticle

  5. Dealkanative main group couplings across the peri-gap

    Taylor, L. J., Buehl, M., Chalmers, B. A., Ray, M. J., Wawrzyniak, P., Walton, J. C., Cordes, D. B., Slawin, A. M. Z., Woollins, J. D. & Kilian, P. 27 Dec 2017 In : Journal of the American Chemical Society. 139, 51, p. 18545-18551

    Research output: Research - peer-reviewArticle

Related by journal

  1. Journal of the American Chemical Society (Journal)

    David Trevor Richens (Editor)
    2005 → …

    Activity: Publication peer-review and editorial workEditor of research journal

ID: 250609895