Skip to content

Research at St Andrews

Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species: vectors to facilitate exploration of two-dimensional chemical space

Research output: Contribution to journalArticlepeer-review

Author(s)

John J. Molloy, Jan B. Metternich, Constantin G. Daniliuc, Allan J. B. Watson, Ryan Gilmour

School/Research organisations

Abstract

Designing strategies to access stereodefined olefinic organoboron species is an important synthetic challenge. Despite significant advances, there is a striking paucity of routes to Z-α-substituted styrenyl organoborons. Herein, this strategic imbalance is redressed by exploiting the polarity of the C(sp2)−B bond to activate the neighboring π system, thus enabling a mild, traceless photocatalytic isomerization of readily accessible E-α-substituted styrenyl BPins to generate the corresponding Z-isomers with high fidelity. Preliminary validation of this contra-thermodynamic E→Z isomerization is demonstrated in a series of stereoretentive transformations to generate Z-configured trisubstituted alkenes, as well as in a concise synthesis of the anti-tumor agent Combretastatin A4.
Close

Details

Original languageEnglish
Pages (from-to)3168-3172
JournalAngewandte Chemie International Edition
Volume57
Issue number12
Early online date21 Feb 2018
DOIs
Publication statusPublished - 12 Mar 2018

    Research areas

  • Alkenes, Boron, Conformational analysis, Isomerizations, Natural products

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

View graph of relations

Related by author

  1. Cu(OTf)2-mediated cross-coupling of nitriles and N-heterocycles with arylboronic acids to generate nitrilium and pyridinium products

    Bell, N., Xu, C., Fyfe, J., Vantourout, J. C., Brals, J., Chabbra, S., Bode, B. E., Cordes, D. B., Slawin, A. M. Z., McGuire, T. M. & Watson, A. J. B., 29 Mar 2021, In: Angewandte Chemie International Edition. 60, 14, p. 7935-7940 7 p.

    Research output: Contribution to journalArticlepeer-review

  2. In vivo half-life extension of BMP1/TLL metalloproteinase inhibitors using small-molecule human serum albumin binders

    Vantourout, J. C., Mason, A. M., Yuen, J., Simpson, G. L., Evindar, G., Kuai, L., Hobbs, M., Edgar, E., Needle, S., Bai, X., Wilson, S., Scott-Stevens, P., Traylen, W., Lambert, K., Young, N., Bunally, S., Summerfield, S. G., Snell, R., Lad, R., Shi, E. & 13 others, Skinner, S., Shewchuk, L., Watson, A. J. B., Chung, C-W., Pal, S., Holt, D. A., Kallander, L. S., Prendergast, J., Rivera, K., Washburn, D. G., Harpel, M. R., Arico-Muendel, C. & Isidro-Llobet, A., 17 Feb 2021, In: Bioconjugate Chemistry. 32, 2

    Research output: Contribution to journalArticlepeer-review

  3. First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst

    Chabbra, S., Smith, D. M., Bell, N. L., Watson, A. J. B., Buehl, M., Cole-Hamilton, D. J. & Bode, B. E., 18 Dec 2020, In: Science Advances. 6, 51, 7 p., eabd7057.

    Research output: Contribution to journalArticlepeer-review

  4. Catalytic enantioselective synthesis of heterocyclic vicinal fluoroamines using asymmetric protonation: a method development and mechanistic study

    Ashford, M., Xu, C., Molloy, J. J., Carpenter-Warren, C. L., Slawin, A. M. Z., Leach, A. G. & Watson, A. J. B., 21 Sep 2020, In: Chemistry - A European Journal. 26, 53, p. 12249-12255 8 p.

    Research output: Contribution to journalArticlepeer-review

  5. Deoxyfluorination using CuF2: enabled by a Lewis base activating group strategy

    Sood, D. E., Champion, S., Dawson, D. M., Chabbra, S., Bode, B. E., Sutherland, A. C. & Watson, A. J. B., 18 May 2020, In: Angewandte Chemie International Edition. 55, 22, p. 8460-8463

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Cu(OTf)2-mediated cross-coupling of nitriles and N-heterocycles with arylboronic acids to generate nitrilium and pyridinium products

    Bell, N., Xu, C., Fyfe, J., Vantourout, J. C., Brals, J., Chabbra, S., Bode, B. E., Cordes, D. B., Slawin, A. M. Z., McGuire, T. M. & Watson, A. J. B., 29 Mar 2021, In: Angewandte Chemie International Edition. 60, 14, p. 7935-7940 7 p.

    Research output: Contribution to journalArticlepeer-review

  2. Enantioselective synthesis of α-aryl-β2-amino-esters via cooperative isothiourea and Brønsted acid catalysis

    Smith, A. D., Zhao, F., Shu, C., Young, C. M., Carpenter-Warren, C. & Slawin, A. M. Z., Mar 2021, In: Angewandte Chemie International Edition. In press

    Research output: Contribution to journalArticlepeer-review

  3. Engineering of a peptide α-N-methyltransferase to methylate non-proteinogenic amino acids

    Naismith, J. H., Song, H., Burton, A. J., Shirran, S. L., Fahrig-Kamarauskaitė, J., Kaspar, H., Muir, T. W. & Künzler, M., 14 Apr 2021, (Accepted/In press) In: Angewandte Chemie International Edition.

    Research output: Contribution to journalArticlepeer-review

  4. Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter

    Rajamalli, P., Rizzi, F., Li, W., Jinks, M. A., Gupta, A. K., Laidlaw, B., Samuel, I. D. W., Penfold, T. J., Goldup, S. M. & Zysman-Colman, E., 5 Mar 2021, In: Angewandte Chemie International Edition.

    Research output: Contribution to journalArticlepeer-review

  5. Controlling single molecule conductance by a locally induced chemical reaction on individual thiophene units

    Michnowicz, T., Borca, B., Pétuya, R., Schendel, V., Pristl, M., Pentegov, I., Kraft, U., Klauk, H., Wahl, P., Mutombo, P., Jelínek, P., Arnau, A., Schlickum, U. & Kern, K., 18 Feb 2020, In: Angewandte Chemie International Edition. In press, 7 p.

    Research output: Contribution to journalArticlepeer-review

ID: 252373767

Top