Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
5 years ago

Contra-Thermodynamic, Photocatalytic EZ Isomerization of Styrenyl Boron Species: Vectors to Facilitate Exploration of 2D Chemical Space

John Molloy, Jan Metternich, Ryan Gilmour, Allan Watson
The high efficiency and stereospecificity of cross-coupling utilizing olefinic organoboron nucleophiles has been a key development in the interrogation of 2D and, following stereoselective elaboration, 3D chemical space. Accordingly, designing strategies to access stereodefined olefinic organoboron species is an important synthetic challenge. However, there is a striking paucity of routes to Z-α-substituted styrenyl organoborons. Herein, we redress this strategic imbalance by exploiting the polarity of the C(sp2)-B bond to activate the neighboring π-system: This enables 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 EZ isomerization is demonstrated via a series of stereoretentive transformations to generate Z-configured tri-substituted alkenes, as well as in a concise synthesis of Combretastatin A-4.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201800286

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