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The Origin of Anion-π Autocatalysis.

ABSTRACT: The autocatalysis of epoxide-opening ether cyclizations on the aromatic surface of anion-π catalysts stands out as a leading example of emergent properties expected from the integration of unorthodox interactions into catalysis. A working hypothesis was proposed early on, but the mechanism of anion-π autocatalysis has never been elucidated. Here, we show that anion-π autocatalysis is almost independent of peripheral crowding in substrate and product. Inaccessible asymmetric anion-π autocatalysis and sometimes erratic reproducibility further support that the origin of anion-π autocatalysis is more complex than originally assumed. The apparent long-distance communication without physical contact calls for the inclusion of water between substrate and product on the catalytic aromatic surface. Efficient anion-π autocatalysis around equimolar amounts but poor activity in dry solvents and with excess water indicate that this inclusion of water requires high precision. Computational models suggest that two water molecules transmit dual substrate activation by the product and serve as proton shuttles along antiparallel but decoupled hydrogen-bonded chains to delocalize and stabilize evolving charge density in the transition state by "anion-π double bonds". This new transition-state model of anion-π autocatalysis provides a plausible mechanism that explains experimental results and brings anion-π catalysis to an unprecedented level of sophistication.

SUBMITTER: Gutierrez Lopez MA

PROVIDER: S-EPMC10131205 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

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The Origin of Anion-π Autocatalysis.

Gutiérrez López M Ángeles MÁ Tan Mei-Ling ML Frontera Antonio A Matile Stefan S

JACS Au 20230317 4

The autocatalysis of epoxide-opening ether cyclizations on the aromatic surface of anion-π catalysts stands out as a leading example of emergent properties expected from the integration of unorthodox interactions into catalysis. A working hypothesis was proposed early on, but the mechanism of anion-π autocatalysis has never been elucidated. Here, we show that anion-π autocatalysis is almost independent of peripheral crowding in substrate and product. Inaccessible asymmetric anion-π autocatalysis ...[more]

PMID: 37124310

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Project description:Substituents alter the electron density distribution in benzene in various ways, depending on their electron withdrawing and donating capabilities, as summarized by the empirical Hammett equation. The change of the π electron density distribution subsequently impacts the interaction of substituted benzenes or other cyclic conjugated rings with anions. Currently the design and synthesis of conjugated cyclic receptors capable of binding anions is an active field due to their applications in the sensing and removal of environmental contaminants and molecular recognition. By using the block-localized wavefunction (BLW) method, which is a variant of ab initio valence bond (VB) theory and can derive the reference resonance-free state self-consistently, we quantified the resonance-assisted (RA) or resonance-impaired (RI) phenomena in anion-π interactions from both structural and energetic perspectives. The frozen interaction, in which the electrostatic attraction is involved, has been shown to be the governing factor for the RA or RI interactions with anions. Energy analyses based on the empirical point charge (EPC) model indicated that the anion-π interactions can be simplified as the attraction between a negative point charge (anion) and a group of local dipoles, affected by the enriched or diminished π-cloud due to the resonance between the substituents and the conjugated ring. Hence, two strategies for the design of novel anion receptors can be envisioned. One is the enhancement of the magnitudes and/or numbers of local dipoles (polarized σ bonds), and the other is the reduction of π electron density in conjugated rings. For cases with the RI characteristics, "curved" aromatic molecules are preferred to be anion receptors. Indeed, extremely strong binding was found in complexes formed with fluorinated corannulene (F-CDD) and fluorinated [5]cycloparaphenylene (F-[5]CPP). Inspired by the RA phenomenon, complexes of p-, o- and m-benzoquinones with halides were revisited.

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The Origin of Anion-π Autocatalysis.

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The Origin of Anion-π Autocatalysis.

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