Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species : vectors to facilitate exploration of two-dimensional chemical space
Date
12/03/2018Metadata
Show full item recordAbstract
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.
Citation
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
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
ISSN
1521-3773Type
Journal article
Description
We 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.Collections
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