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

Research output: Contribution to journalArticle

Author(s)

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

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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.
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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

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