In spite of their potential utility, the chemistry of dimetalated arenes is still in its infancy because they are extremely difficult to synthesize. We report a novel method of synthesizing arenes bearing a boryl group and a metallic substituent, such as boryl, silyl, stannyl, or zincyl groups, in an integrated flow microreactor based on the generation and reactions of aryllithiums bearing a trialkyl borate moiety. The bimetallic arenes showed a remarkable chemoselectivity in palladium-catalyzed cross-coupling reactions. The selectivity was switched by the selection of the metal species that constitutes the dimetalated arenes as well as appropriate catalysts.
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Facile Access to Hetero-poly-functional Arenes and meta-Substituted Arenes via Two-Step Dimetalation and Mg/Halogen-Exchange Protocol.
Chemistry
February 2021
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, Scotland.
Article Synopsis
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A Synthetic Approach to Dimetalated Arenes Using Flow Microreactors and the Switchable Application to Chemoselective Cross-Coupling Reactions.
J Am Chem Soc
October 2020
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigakukatsura Nishikyo-ku, Kyoto 615-8510, Japan.
In spite of their potential utility, the chemistry of dimetalated arenes is still in its infancy because they are extremely difficult to synthesize. We report a novel method of synthesizing arenes bearing a boryl group and a metallic substituent, such as boryl, silyl, stannyl, or zincyl groups, in an integrated flow microreactor based on the generation and reactions of aryllithiums bearing a trialkyl borate moiety. The bimetallic arenes showed a remarkable chemoselectivity in palladium-catalyzed cross-coupling reactions.
View Article and Find Full Text PDFStrong bases. Directed ortho-meta'- and meta-meta'-dimetalations: a template base approach to deprotonation.
Science
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WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK.
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View Article and Find Full Text PDFCleavage of carbon-carbon bonds in aromatic nitriles using nickel(0).
J Am Chem Soc
August 2002
Contribution from the Facultad de Química, Universidad Nacional Autónoma de México, México, D.F. 04510.
The nickel(0) fragment [(dippe)Ni] has been found to react with a variety of aromatic nitriles. Initial pi-coordination to the C=C and Ctbd1;N bonds of 2-cyanoquinoline is found to lead ultimately to C-CN oxidative addition. 3-Cyanoquinoline reacts similarly, although no eta(2)-CN complex is observed.
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