Organic Photoredox-Catalyzed Cycloadditions Under Single-Chain Polymer Confinement

Abstract

<jats:p>Cooperative catalysis enables synthetic transformations that are not feasible using monocatalytic systems. Such reactions are often diffusion controlled and require multiple catalyst interactions at high dilution. We developed a confined dual-catalytic polymer nanoreactor that enforces catalyst co-localization to enhance reactivity in a fully-homogeneous system. The photocatalyzed-dimerization of substituted styrenes is disclosed using confined-single-chain polymers bearing triarylpyrylium-based pendants, with pyrene as an electron relay catalyst. Enhanced reactivity with low catalyst loadings was observed compared to monocatalytic polymers with small-molecule additives. Our approach realizes a dual-catalytic single-chain polymer that provides enhanced reactivity under confinement, presenting a further approach for diffusion-limited-photoredox catalysis.</jats:p>