Compartmentalised carbonylation cascade initiated by photocatalytic CO 2 reduction Sampurna Mitra , David Vahey, Shannon A. Bonke, Erwin Reisner Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB2 1EW, UK Photocatalytic CO 2 reduction is a sustainable approach to produce CO, which is an important platform molecule to synthesise many important chemicals. Utilisation of CO 2 as a carbon source in the production of complex chemicals mimics photosynthesis and produces high-value products. Herein, we demonstrate a biomimetic reaction cascade of photocatalytic CO 2 reduction followed by carbonylation reactions that directly use the in situ generated CO. Solvent layering is used to create separated environments for CO 2 reduction and carbonylation reactions, enabling photocatalytic CO 2 reduction in aqueous media that produces CO, which moves into the more buoyant toluene layer wherein it is utilised in Pd-catalysed Buchwald-Hartwig aminocarbonylation, Sonogashira alkyne coupling, and carbonylative Suzuki coupling. The aqueous CO 2 to CO conversion is enabled by water-soluble cobalt porphyrins paired with either ruthenium or copper dyes, while the organic layer utilises a Pd-Xantphos carbonylation catalyst to produce a variety of products in good yields (70%). Sonogashira and carbonylative Suzuki couplings are demonstrated alongside the synthesis of a pharmaceutical (Itopride). This work represents the first photocatalytic cascade for the direct utilisation of CO 2 as a carbon source for pharmaceutical production, enabled by biomimetic reaction compartmentalisation.
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