Skip to content

Research at St Andrews

Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis

Research output: Contribution to journalArticle

Author(s)

Anastassia Matviitsuk, Mark Greenhalgh, Diego Barrios Antunez, Alexandra Slawin, Andrew David Smith

School/Research organisations

Abstract

A new general concept for α,β-unsaturated acyl ammonium catalysis is reported that uses p-nitrophenoxide release from an α,β-unsaturated p-nitrophenyl ester substrate to facilitate catalyst turnover. This method was used for the enantioselective isothiourea-catalyzed Michael addition of nitroalkanes to α,β-unsaturated p-nitrophenyl esters in generally good yield and with excellent enantioselectivity (27 examples, up to 79% yield, 99:1 er). Mechanistic studies identified rapid and reversible catalyst acylation by the α,β-unsaturated p-nitrophenyl ester, and a recently reported variable-time normalization kinetic analysis method was used to delineate the complex reaction kinetics.
Close

Details

Original languageEnglish
Pages (from-to)12450-12455
Number of pages6
JournalAngewandte Chemie
Volume129
Issue number40
Early online date25 Aug 2017
DOIs
Publication statusPublished - 25 Sep 2017

    Research areas

  • Lewis base catalysis, α,β-unsaturated ammonium, Isothiourea, Aryloxide catalyst turnover, Kinetic and mechanistic analysis

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

View graph of relations

Related by author

  1. Tandem sequential catalytic enantioselective synthesis of highly-functionalised tetrahydroindolizine derivatives

    Zhang, S., Greenhalgh, M. D., Slawin, A. M. Z. & Smith, A. D., 12 Mar 2020, In : Chemical Science. Advance Article, 8 p.

    Research output: Contribution to journalArticle

  2. Isothiourea-catalyzed atropselective acylation of biaryl phenols via sequential desymmetrization/kinetic resolution

    Munday, E. S., Grove, M., Feoktistova, T., Brueckner, A. C., Walden, D., Young, C. M., Slawin, A. M. Z., Campbell, A., Cheong, P. H-Y. & Smith, A. D., 11 Mar 2020, In : Angewandte Chemie International Edition. Early View

    Research output: Contribution to journalArticle

  3. Isothiourea-catalyzed enantioselective synthesis of tetrahydro-α-carbolinones

    Liu, H., Slawin, A. M. M. & Smith, A. D., 6 Feb 2020, In : Organic Letters. Articles ASAP

    Research output: Contribution to journalArticle

  4. The importance of 1,5-oxygen···chalcogen interactions in enantioselective isochalcogenourea catalysis

    Young, C. M., Elmi, A., Pascoe, D. J., Morris, R. K., McLaughlin, C., Woods, A., Frost, A., De La Houpliere, A., Ling, K. B., Smith, T. K., Slawin, A. M. Z., Willoughby, P. H., Cockroft, S. L. & Smith, A. D., 3 Feb 2020, In : Angewandte Chemie International Edition. Early View

    Research output: Contribution to journalArticle

Related by journal

  1. Angewandte Chemie (Journal)

    J Derek Woollins (Editor)
    2005 → …

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

Related by journal

  1. Sub-micromolar pulse dipolar EPR spectroscopy reveals increasing CuII-labelling of double-histidine motifs with lower temperature

    Wort, J., Ackermann, K., Giannoulis, A., Stewart, A. J., Norman, D. & Bode, B. E., 19 Aug 2019, In : Angewandte Chemie. 131, 34, p. 11807-11811 6 p.

    Research output: Contribution to journalArticle

  2. A highly active manganese catalyst for enantioselective ketone and ester hydrogenation

    Widegren, M. B., Harkness, G. J., Slawin, A. M. Z., Cordes, D. B. & Clarke, M. L., 15 May 2017, In : Angewandte Chemie. 129, 21, p. 5919-5922 4 p.

    Research output: Contribution to journalArticle

  3. Enzyme activity by design: an artificial rhodium hydroformylase for linear aldehydes

    Jarvis, A., Obrecht, L., Deuss, P., Laan, W., Gibson, E. K., Wells, P. P. & Kamer, P. C. J., 23 Oct 2017, In : Angewandte Chemie. 129, 44, p. 13784-13788

    Research output: Contribution to journalArticle

  4. Expansion of the ADOR strategy for the synthesis of new zeolites: the synthesis of IPC-12 from zeolite UOV

    Kasneryk, V., Shamzhy, M., Opanasenko, M., Wheatley, P. S., Morris, S. A., Russell, S. E., Mayoral, A., Trachta, M., Čejka, J. & Morris, R. E., 3 Apr 2017, In : Angewandte Chemie. 56, 15, p. 4324-4327 5 p.

    Research output: Contribution to journalArticle

ID: 250595435

Top