Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species : vectors to facilitate exploration of two-dimensional chemical space
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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.
Molloy , J J , Metternich , J B , Daniliuc , C G , Watson , A J B & Gilmour , R 2018 , ' Contra -thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species : vectors to facilitate exploration of two-dimensional chemical space ' Angewandte Chemie International Edition , vol. 57 , no. 12 , pp. 3168-3172 . https://doi.org/10.1002/anie.201800286
Angewandte Chemie International Edition
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/anie.201800286
DescriptionWe acknowledge financial support from the WWU Münster, Deutsche Forschungsgemeinschaft (Excellence Cluster EXC 1003), and Fonds der Chemischen Industrie (Fellowship to JBM). JJM was supported by a PEER/PECRE award by WestChem and the Scottish Funding Council.
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