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 colocalization to enhance reactivity in a fully homogeneous system. The photoredox-catalyzed 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 and analogous small molecules. Our approach realizes a dual-catalytic single-chain polymer that provides enhanced reactivity under confinement, presenting a further approach for diffusion-limited-photoredox catalysis.
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