Probing the Lewis Acidity of Boronic Acids through Interactions with Arene Substituents

Jie Jian, Roel Hammink, Christine J. McKenzie, F. Matthias Bickelhaupt, Jordi Poater, Jasmin Mecinović*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Boronic acids are Lewis acids that exist in equilibrium with boronate forms in aqueous solution. Here we experimentally and computationally investigated the Lewis acidity of 2,6-diarylphenylboronic acids; specially designed phenylboronic acids that possess two flanking aromatic rings with tunable aromatic character. Hammett analysis of 2,6-diarylphenylboronic acids reveals that their Lewis acidity remains unchanged upon the introduction of EWG/EDG at the distant para position of the flanking aromatic rings. Structural and computational studies demonstrate that polar-π interactions and solvation effects contribute to the stabilization of boronic acids and boronate forms by aromatic rings. Our physical-organic chemistry work highlights that boronic acids and boronates can be stabilized by aromatic systems, leading to an important molecular knowledge for rational design and development of boronic acid-based catalysts and inhibitors of biomedically important proteins.

Original languageEnglish
Article numbere202104044
Pages (from-to)1-7
Number of pages7
JournalChemistry - A European Journal
Volume28
Issue number9
Early online date27 Dec 2021
DOIs
Publication statusPublished - 16 Feb 2022

Bibliographical note

Funding Information:
J.J. thanks the China Scholarship Council (CSC201808440511). F.M.B. acknowledges the Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (PID‐2019‐106830GB‐I00 and MDM‐2017‐0767) and the Generalitat de Catalunya (2017SGR348). The Carlsberg Foundation is acknowledged for funding for the X‐ray diffractometer (grant CF15‐0675). We thank Christian Jørgensen for help with the NMR measurements.

Funding Information:
J.J. thanks the China Scholarship Council (CSC201808440511). F.M.B. acknowledges the Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (PID-2019-106830GB-I00 and MDM-2017-0767) and the Generalitat de Catalunya (2017SGR348). The Carlsberg Foundation is acknowledged for funding for the X-ray diffractometer (grant CF15-0675). We thank Christian J?rgensen for help with the NMR measurements.

Publisher Copyright:
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

Keywords

  • aromatic compounds
  • boronic acids
  • Lewis acidity
  • non-covalent interactions
  • polar-π interactions

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