Article

Protecting Group-Free Photocatalyzed O-Arylation of Quinic Acid

Tetrahedron Green Chem

Miguel A. Bárbara; Nuno R. Candeias; Carlos A. M. Afonso — 2025 — Elsevier

Key information

Authors:

Miguel A. Bárbara; Nuno R. Candeias; Luis F. Veiros (Luís Filipe Coelho Veiros); Filipe Menezes; Andrea Gualandi; Pier G. Cozzi; Carlos A. M. Afonso

Published in

06/01/2025

Abstract

This study presents a novel and environmentally friendly approach to the preparation of quinic acid-derived esters from photocatalyzed O-arylation with haloarenes. This study expands the quinic acid-derived chemical space from renewable biomass by harnessing the power of visible-light-driven photocatalysis under mild conditions without the need for protecting groups. A thorough screening of reaction conditions, including the choice of photocatalyst, solvent, base, nickel source, and ligand, led to the identification of the most effective conditions, these being 5CzBN as the optimal photocatalyst, and glyme-based nickel complexes as the preferred nickel source. These conditions enabled the formation of O-arylated products with good yields without noticeable formation of decarboxylated products. Computational calculations support the proposed mechanism for the O-arylation process, based on oxidative addition, anion exchange, and reductive elimination upon energy transfer from the photocatalyst to the Ni(II) species. Computational considerations for a nickel-catalyzed photodecarboxylative arylation mechanism suggest that the oxidation of quinate by the excited photocatalyst or other species derived thereof is considerably less favorable than a pathway only involving energy transfer to a nickel species. The research provides valuable insights into the mechanism of this environmentally conscious transformation.

Publication details

Authors in the community:

Publication version

VoR - Version of Record

Publisher

Elsevier

Link to the publisher's version

https://www.sciencedirect.com/science/article/pii/S2773223125000093?via%3Dihub

Title of the publication container

Tetrahedron Green Chem

First page or article number

100070

Last page

100070-10

Volume

5

Issue

1

ISSN

2773-2231

DOI

10.1016/j.tgchem.2025.100070

Fields of Science and Technology (FOS)

chemical-sciences - Chemical sciences

Keywords

  • Quinic acid
  • Photoredox
  • Polyols
  • Coupling
  • DFT calculations
  • Photocatalysis

Publication language (ISO code)

eng - English

Rights type:

Only metadata available

Creative Commons license

CC-BY-NC-ND - CC-BY-NC-ND