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Contra‐Thermodynamic, Photocatalytic E → Z Isomerization of Styrenyl Boron Species: Vectors to Facilitate Exploration of Two‐Dimensional Chemical Space
Author(s) -
Molloy John J.,
Metternich Jan B.,
Daniliuc Constantin G.,
Watson Allan J. B.,
Gilmour Ryan
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201800286
Subject(s) - isomerization , chemistry , photocatalysis , chemical space , boron , process (computing) , computational chemistry , combinatorial chemistry , catalysis , computer science , organic chemistry , biochemistry , drug discovery , operating system
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(sp 2 )−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.