Visible Light Excitation of Poly‐(<i>para</i>‐Phenylene Ethynylene) Enables Heterogeneous Photocatalytic Oxidations of Amines in Flow

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.