Skip to content

Research at St Andrews

Exploring the scope of tandem palladium and isothiourea relay catalysis for the synthesis of α-amino acid derivatives

Research output: Contribution to journalArticlepeer-review

Author(s)

School/Research organisations

Abstract

The scope and limitations of a tandem N-allylation/[2,3]-rearrangementprotocol are investigated through the incorporation of a variety of functionalgroups within an allylic phosphate precursor. This method uses readilyaccessible N,N-dimethylglycine aryl esters and functionalizedallylic phosphates, forming quaternary ammonium salts in situ in the presence of a palladium catalyst. Subsequentenantioselective [2,3]-sigmatropic rearrangement, promoted by the chiralisothiourea tetramisole, generates α-amino acid derivatives with two contiguousstereocenters. The incorporation of electron withdrawing ester and amide groupsgave the best results, furnishing the desired products in moderate to goodyields (29-70%), with low diastereocontrol (typically 60:40 dr) but highenantioselectivity (up to 90:10 er). These results indicate that substrate-catalystinteractions in the proposed transition state are sensitive to the substitutionpattern of the substrates.
Close

Details

Original languageEnglish
Article number2463
Number of pages13
JournalMolecules
Volume25
Issue number10
DOIs
Publication statusPublished - 25 May 2020

    Research areas

  • Isothiourea, Palladium, Enantioselective catalysis, Amino acids, [2,3]-rearrangement, N-allylation

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

View graph of relations

Related by author

  1. Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates

    Matviitsuk, A., Greenhalgh, M. D., Taylor, J. E., Nguyen, X. B., Cordes, D. B., Slawin, A. M. Z., Lupton, D. W. & Smith, A. D., 23 Dec 2019, In: Organic Letters. Article ASAP

    Research output: Contribution to journalArticlepeer-review

  2. Synthesis of fused indoline-cyclobutanone derivatives via an intramolecular [2+2] cycloaddition

    Neyyappadath, R. M., Greenhalgh, M. D., Cordes, D. B., Slawin, A. M. Z. & Smith, A. D., 12 Apr 2019, In: European Journal of Organic Chemistry. Early View

    Research output: Contribution to journalArticlepeer-review

  3. Chiral AuI- and AuIII-isothiourea complexes: synthesis, characterization and application

    Gasperini, D., Greenhalgh, M., Imad, R., Siddiqui, S., Malik, A., Arshad, F., Choudhary, M. I., Al-Majid, A., Cordes, D., Slawin, A., Nolan, S. & Smith, A. D., 21 Dec 2018, In: Chemistry - A European Journal. Early View

    Research output: Contribution to journalArticlepeer-review

  4. 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 7 p.

    Research output: Contribution to journalArticlepeer-review

  5. 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 journalArticlepeer-review

Related by journal

  1. Biogenic gold nanoparticles decrease methylene blue photobleaching and enhance antimicrobial photodynamic therapy

    Maliszewska, I., Wanarska, E., Thompson, A. C., Samuel, I. D. W. & Matczyszyn, K., 25 Jan 2021, In: Molecules. 26, 3, 16 p., 623.

    Research output: Contribution to journalArticlepeer-review

  2. Synthesis and single crystal structures of N-substituted benzamides and their chemoselective selenation/reduction derivatives

    Hua, G., Carpenter-Warren, C. L., Cordes, D. B., Slawin, A. M. Z. & Woollins, J. D., 19 Apr 2021, In: Molecules. 26, 8, 10 p., 2367.

    Research output: Contribution to journalArticlepeer-review

  3. Free radical mediated oxidative degradation of carotenes and xanthophylls

    Mordi, R. C., Ademosun, O. T., Ajanaku, C. O., Olanrewaju, I. O. & Walton, J. C., 26 Feb 2020, In: Molecules. 25, 5, 13 p., 1038.

    Research output: Contribution to journalReview articlepeer-review

  4. Parameters for irreversible inactivation of monoamine oxidase

    Ramsay, R. R., Basile, L., Maniquet, A., Hagenow, S., Pappalardo, M., Saija, M. C., Bryant, S., Albreht, A. & Guccione, S., 13 Dec 2020, In: Molecules. 25, 24, 25 p., 5908.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Molecules (Journal)

    Ross Gillanders (Member of editorial board)

    Oct 2019 → …

    Activity: Publication peer-review and editorial work typesPeer review of manuscripts

  2. Molecules (Journal)

    John Christopher Walton (Member of editorial board)

    10 May 2016

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

  3. Molecules (Journal)

    John Christopher Walton (Member of editorial board)

    31 Aug 2014

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

  4. Molecules (Journal)

    John Christopher Walton (Member of editorial board)

    20132018

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

ID: 268098165

Top