Cobalt(III) Halide Metal-Organic Frameworks Drive Catalytic Halogen Exchange

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Apr 12

PMID 38607314

Authors

Tyler J Azbell

Phillip J Milner

Affiliations

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Abstract

The selective halogenation of complex (hetero)aromatic systems is a critical yet challenging transformation that is relevant to medicinal chemistry, agriculture, and biomedical imaging. However, current methods are limited by toxic reagents, expensive homogeneous second- and third-row transition metal catalysts, or poor substrate tolerance. Herein, we demonstrate that porous metal-organic frameworks (MOFs) containing terminal Co(III) halide sites represent a rare and general class of heterogeneous catalysts for the controlled installation of chlorine and fluorine centers into electron-deficient (hetero)aryl bromides using simple metal halide salts. Mechanistic studies support that these halogen exchange (halex) reactions proceed via redox-neutral nucleophilic aromatic substitution (SAr) at the Co(III) sites. The MOF-based halex catalysts are recyclable, enable green halogenation with minimal waste generation, and facilitate halex in a continuous flow. Our findings represent the first example of SAr catalysis using MOFs, expanding the lexicon of synthetic transformations enabled by these materials.

Citing Articles

Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks.

Kong X, He T, Bezrukov A, Darwish S, Si G, Zhang Y J Am Chem Soc. 2024; .

PMID: 39376039 PMC: 11487582. DOI: 10.1021/jacs.4c09173.

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