A Self‐Sustaining Supramolecular (Auto)Photocatalysis via the Synthesis of <i>N</i> ‐Vinylacetamides

Efforts to enhance photocatalysts prioritize improving their accessibility and practicality in photocatalytic applications. Supramolecular (auto)photocatalysis, which exploits transient self-assembled complexes, facilitates visible light-driven reactions, with autocatalytic systems promoting sustainable and atom-economical processes. In this study, the photocatalyst Mes-Acr-MeClO₄, typically active under blue light, formed a dark red charge-transfer (CT) complex with N-bromoacetamide (NBA) in the presence of K₂CO₃ in DCE, enabling green-light photocatalysis. This self-assembled CT complex initiated an auto-photocatalytic process via two-photon absorption, generating an N-centered radical that drove anti-Markovnikov, syn-periplanar addition to phenylacetylene, achieving exclusive Z-selective formation of (Z)-N-(2-bromo-2-phenylvinyl)acetamide. Interestingly, the product itself functioned as a potent green-LED photocatalyst (λ_em = 518 nm, τ = 10 ns), driving its own synthesis with added terminal alkynes. With 100% atom economy, this work highlights a system chemistry approach, showcasing a highly efficient, self-sustaining catalytic process that advances green and sustainable synthetic strategies. This protocol emphasizes sustainability with an outstanding E-factor of 11.15, reflecting minimal waste production (11.15 kg per 1 kg of product) and demonstrating a strong commitment to green chemistry principles.