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Synthesis of 3,5-Dichloro-4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) via Cu(OTf)2 Mediated Oxidative Nucleophilic Substitution of Hydrogen by Chloride

Lookup NU author(s): Abdu Alsimaree, Dr Paul Waddell, Dr Mike ProbertORCiD, Dr Thomas Penfold, Dr Julian Knight, Dr Michael HallORCiD

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This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND).


Abstract

Regioselective halogenation is often a key step in the formation of substituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophores, through the enablement of subsequent downstream C-C or C-X bond forming steps via SNAr or metal catalyzed cross-coupling reactions. Classical SEAr halogenation of unsubstituted BODIPYs results in 2/6-substitution, precluding easy access to 3/5-halogenated BODIPYs. Herein we present our development of a 3,5-dihalogenation reaction of unsubstituted BODIPYs, via a double oxidative nucleophilic substitution of hydrogen with chloride. Reaction of a range of meso-aryl, but otherwise unsubstituted, BODIPYs with stoichiometric Cu(OTf)2 in the presence of ethanolamine and tetrabutylammonium chloride gives high isolated yields of the corresponding 3,5-dichlorinated BODIPYs, facilitating access to these valuable synthetic intermediates.


Publication metadata

Author(s): Frank F, Manzoli LA, Mauker P, Alsimaree AA, Waddell PG, Probert MR, Penfold TJ, Knight JG, Hall MJ

Publication type: Article

Publication status: Published

Journal: Tetrahedron

Year: 2020

Volume: 76

Issue: 17

Print publication date: 24/04/2020

Online publication date: 13/03/2020

Acceptance date: 06/03/2020

Date deposited: 07/03/2020

ISSN (print): 0040-4020

ISSN (electronic): 1464-5416

Publisher: Elsevier Ltd

URL: https://doi.org/10.1016/j.tet.2020.131113

DOI: 10.1016/j.tet.2020.131113


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Funding

Funder referenceFunder name
EP/F03637X/1EPSRC

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