Protecting group-free photocatalyzed O-arylation of quinic acid
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 photoca...
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| Format: | Article |
| Language: | English |
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Elsevier
2025-06-01
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| Series: | Tetrahedron Green Chem |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2773223125000093 |
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| author | Miguel A. Bárbara Nuno R. Candeias Luis F. Veiros Filipe Menezes Andrea Gualandi Pier G. Cozzi Carlos A.M. Afonso |
| author_facet | Miguel A. Bárbara Nuno R. Candeias Luis F. Veiros Filipe Menezes Andrea Gualandi Pier G. Cozzi Carlos A.M. Afonso |
| author_sort | Miguel A. Bárbara |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-939aa43a47e448e6978bd64ee3e2e199 |
| institution | OA Journals |
| issn | 2773-2231 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Tetrahedron Green Chem |
| spelling | doaj-art-939aa43a47e448e6978bd64ee3e2e1992025-08-20T02:06:20ZengElsevierTetrahedron Green Chem2773-22312025-06-01510007010.1016/j.tgchem.2025.100070Protecting group-free photocatalyzed O-arylation of quinic acidMiguel A. Bárbara0Nuno R. Candeias1Luis F. Veiros2Filipe Menezes3Andrea Gualandi4Pier G. Cozzi5Carlos A.M. Afonso6Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003, Lisbon, PortugalLAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal; Faculty of Engineering and Natural Sciences, Tampere University, Korkeakoulunkatu 8, 33101, Tampere, Finland; Corresponding author. LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal.Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049 001, Lisboa, PortugalHelmholtz Munich, Molecular Targets and Therapeutics Center, Institute of Structural Biology, Ingolstädter Landstr. 1, 85764, Neuherberg, GermanyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum—Università di Bologna, Via Gobetti 85, 40129, Bologna, Italy; Center for Chemical Catalysis – C3, Alma Mater Studiorum – Università di Bologna, Via Gobetti 85, 40129, Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum—Università di Bologna, Via Gobetti 85, 40129, Bologna, ItalyResearch Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003, Lisbon, Portugal; Corresponding author. Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003, Lisbon, Portugal.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.http://www.sciencedirect.com/science/article/pii/S2773223125000093Quinic acidPhotoredoxPolyolsCouplingDFT calculationsPhotocatalysis |
| spellingShingle | Miguel A. Bárbara Nuno R. Candeias Luis F. Veiros Filipe Menezes Andrea Gualandi Pier G. Cozzi Carlos A.M. Afonso Protecting group-free photocatalyzed O-arylation of quinic acid Tetrahedron Green Chem Quinic acid Photoredox Polyols Coupling DFT calculations Photocatalysis |
| title | Protecting group-free photocatalyzed O-arylation of quinic acid |
| title_full | Protecting group-free photocatalyzed O-arylation of quinic acid |
| title_fullStr | Protecting group-free photocatalyzed O-arylation of quinic acid |
| title_full_unstemmed | Protecting group-free photocatalyzed O-arylation of quinic acid |
| title_short | Protecting group-free photocatalyzed O-arylation of quinic acid |
| title_sort | protecting group free photocatalyzed o arylation of quinic acid |
| topic | Quinic acid Photoredox Polyols Coupling DFT calculations Photocatalysis |
| url | http://www.sciencedirect.com/science/article/pii/S2773223125000093 |
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