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

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

doi:10.1002/anie.201800286

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

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

School of Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	3168-3172
Journal	Angewandte Chemie International Edition
Volume	57
Issue number	12
Early online date	21 Feb 2018
DOIs	https://doi.org/10.1002/anie.201800286
Publication status	Published - 12 Mar 2018

Keywords

Alkenes
Boron
Conformational analysis
Isomerizations
Natural products

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10.1002/anie.201800286

Molloy_2018_ACIE_2-Dchemicalspace_AAM
© 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
Accepted author manuscript, 1.43 MB

Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species: vectors to facilitate exploration of two-dimensional chemical space (dataset)
Molloy, J. J. (Creator), Metternich, J. B. (Creator), Daniliuc, C. G. (Creator), Watson, A. J. B. (Creator) & Gilmour, R. (Creator), Cambridge Crystallographic Data Centre, 2018
https://dx.doi.org/10.5517/ccdc.csd.cc1yxyld and one more link, https://dx.doi.org/10.5517/ccdc.csd.cc1yxymf (show fewer)
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title = "Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species: vectors to facilitate exploration of two-dimensional chemical space",

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.",

keywords = "Alkenes, Boron, Conformational analysis, Isomerizations, Natural products",

author = "Molloy, {John J.} and Metternich, {Jan B.} and Daniliuc, {Constantin G.} and Watson, {Allan J. B.} and Ryan Gilmour",

note = "We acknowledge financial support from the WWU M{\"u}nster, 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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doi = "10.1002/anie.201800286",

language = "English",

volume = "57",

pages = "3168--3172",

journal = "Angewandte Chemie International Edition",

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Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species: vectors to facilitate exploration of two-dimensional chemical space. / Molloy, John J.; Metternich, Jan B.; Daniliuc, Constantin G. et al.
In: Angewandte Chemie International Edition, Vol. 57, No. 12, 12.03.2018, p. 3168-3172.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Contra-thermodynamic, photocatalytic E→Z isomerization of styrenyl boron species

T2 - vectors to facilitate exploration of two-dimensional chemical space

AU - Molloy, John J.

AU - Metternich, Jan B.

AU - Daniliuc, Constantin G.

AU - Watson, Allan J. B.

AU - Gilmour, Ryan

N1 - 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.

PY - 2018/3/12

Y1 - 2018/3/12

N2 - 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.

AB - 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.

KW - Alkenes

KW - Boron

KW - Conformational analysis

KW - Isomerizations

KW - Natural products

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

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ER -

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

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Keywords

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

Cite this