One‐Pot Biphasic Photocatalytic CO 2 ‐to‐Carbonylation Cascades

ABSTRACT Photosynthesis compartmentalizes reactions across the thylakoid membrane in vivo to upcycle CO 2 into complex chemicals that are fundamental to life. Herein, we demonstrate a step toward achieving a synthetic equivalent to the chloroplast with a compartmentalized cascade reaction in vitro that enables light driven CO 2 utilization for organic synthesis in one‐pot. This bioinspired compartmentalization enables the photocatalytic reduction of aqueous CO 2 by water‐soluble catalysts and dyes to produce CO, which then moves into the more buoyant organic layer and is consumed in aminocarbonylation or carbonylative variants of Sonogashira and Suzuki couplings, including the synthesis of the pharmaceutical itopride. The reaction compartmentalization significantly increases the biomimicry of CO 2 utilization by enabling the light‐driven generation and utilization of CO from CO 2 for chemical synthesis in the same pot compared to previous two‐pot approaches. The fundamental platform and design criteria described herein can enable future reactions to utilize building blocks as abundant as CO 2 to generate complex molecules through bioinspired pathways.