A self-assembled coordination cage enhances the reactivity of confined amides via mechanical bond-twisting

Self-assembled coordination cages composed of metal cations and ligands can enhance the hydrolysis of non-covalently trapped amides in mild conditions as demonstrated in recent experiments. Here, we reveal the mechanism that accelerates base-catalyzed amide hydrolysis inside the octahedral coordinat...

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Published inPhysical chemistry chemical physics : PCCP Vol. 24; no. 35; pp. 21367 - 21371
Main Authors Tamura, Hiroyuki, Takezawa, Hiroki, Fujita, Makoto, Ishikita, Hiroshi
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 14.09.2022
Subjects
Amides
Cages
Continuum modeling
Coordination
Dihedral angle
Hydrolysis
Quantum mechanics
Self-assembly
Twisting
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Summary:Self-assembled coordination cages composed of metal cations and ligands can enhance the hydrolysis of non-covalently trapped amides in mild conditions as demonstrated in recent experiments. Here, we reveal the mechanism that accelerates base-catalyzed amide hydrolysis inside the octahedral coordination cage, by means of a quantum mechanics/molecular mechanics/polarizable continuum model. The calculated activation barrier of the nucleophilic OH − addition to a planar diaryl amide drastically decreases in the cage because of mechanical bond-twisting due to host–guest π-stacking. By contrast, the OH − addition to an N -acylindole, which possesses a twisted amide bond in bulk water, is not enhanced in the cage. Even though the cage hinders OH − collisions with the confined amide, the cage can twist the dihedral angle of the planar amide so as to mimic the transition state of OH − addition.
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ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp03126d