Defect-Engineered Metal–Organic Frameworks as Bioinspired Heterogeneous Catalysts for Amide Bond Formation
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AhmadJACS.pdf
Description
Published version
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1.8 MB
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Author(s)
Ahmad, Bayu IZ
Jerozal, Ronald T
Meng, Sijing
Oh, Changwan
Cho, Yeongsu
Kulik, Heather J
Lambert, Tristan H
Milner, Phillip J
Date Issued
December 4, 2024
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Bayu I. Z. Ahmad, Ronald T. Jerozal, Sijing Meng, Changwan Oh, Yeongsu Cho, Heather J. Kulik, Tristan H. Lambert, and Phillip J. Milner.
Journal of the American Chemical Society 2024 146 (50), 34743-34752.
Version
Author's final manuscript
Abstract
The synthesis of amides from amines and carboxylic
acids is the most widely carried out reaction in medicinal
chemistry. Yet, most amide couplings are still conducted using
stoichiometric reagents, leading to significant waste; few synthetic
catalysts for this transformation have been adopted industrially due
to their limited scope and/or poor recyclability. The majority of
catalytic approaches focus on a single activation mode, such as
enhancing the electrophilicity of the carboxylic acid partner using a
Lewis acid. In contrast, nature effortlessly forges and breaks amide
bonds using precise arrays of Lewis/Brønsted acidic and basic
functional groups. Drawing inspiration from these systems, herein
we report a simple defect engineering strategy to colocalize Lewis acidic Zr sites with other catalytically active species within porous
metal−organic frameworks (MOFs). Specifically, the combination of pyridine N-oxide and Zr open metal sites within the defective
framework MOF-808-py-Nox produces a heterogeneous catalyst that facilitates amide bond formation with broad functional group
compatibility from amines and carboxylic acids, esters, or primary amides. Extensive density functional theory (DFT) calculations
using cluster models support that the formation of a hydrogen-bonding network at the defect sites facilitates amide bond formation
in this material. MOF-808-py-Nox can be recycled at least five times without losing significant crystallinity, porosity, or catalytic
activity and can be employed in continuous flow. This defect engineering strategy can be potentially generalized to produce libraries
of catalytically active MOFs with different combinations of colocalized functional groups.
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DOI of Published Version
https://doi.org/10.1021/jacs.4c13196
