Visible Light Excitation of Poly-(para-Phenylene Ethynylene) Enables Heterogeneous Photocatalytic Oxidations of Amines in Flow.

Autor: Weyl B; Chimie Moléculaire, Macromoléculaire et Matériaux (C3M), UMR CNRS 7167, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., Goujon G; Chimie Moléculaire, Macromoléculaire et Matériaux (C3M), UMR CNRS 7167, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., Raggio L; Chimie Moléculaire, Macromoléculaire et Matériaux (C3M), UMR CNRS 7167, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., Demey E; Spectrométrie de Masse Biologique et Protéomique (SMBP), UMR CNRS 8249, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., Vinh J; Spectrométrie de Masse Biologique et Protéomique (SMBP), UMR CNRS 8249, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., d'Espinose de Lacaillerie JB; Sciences et Ingénierie de la Matière Molle (SIMM), UMR CNRS 7615, Sorbonne Université ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France., Krafft JM; Laboratoire de Réactivité de Surface (LRS), UMR CNRS 7197, Sorbonne Université, 4 place Jussieu, 75005, Paris, France., Laroche B; Chimie Moléculaire, Macromoléculaire et Matériaux (C3M), UMR CNRS 7167, ESPCI Paris PSL, 10 rue Vauquelin, 75005, Paris, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 22, pp. e202419169. Date of Electronic Publication: 2024 Oct 22.
DOI: 10.1002/anie.202419169
Abstrakt: Heterogeneous visible light photocatalysis is a compelling approach to address sustainability in synthetic photochemistry. However, the use of solid-state photocatalysts remains very unpopular in organic synthesis because of their limited accessibility and the black-box effect associated to the lack of rational between their molecular structure and their photochemical properties. Herein, we disclose the synthesis, characterization, photocatalytic properties and synthetic applications of a simple and readily available solid-state conjugated organic polymer, poly-(para-phenylene ethynylene) 1, which exhibits a strong oxidative power upon irradiation with visible light (E(1*/1⋅ - )=+1.67 V vs SCE). Comparisons with structural analogues highlighted the superior photocatalytic activity of this linear semiconductor, on account of its fully conjugated architecture. The associated excited-state reactivity enabled the transformation of various amines into imines in batch and continuous flow reactors together with straightforward photocatalyst recycling. Mechanistic investigations revealed concomitant photoredox and energy transfer pathways, that led to the formation of the desired products. Ultimately, the inline generation of imines was exploited in telescoped three-component Ugi reactions (3CR) in batch and flow toward biologically relevant α-acylaminoamides.
(© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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