An oscillatory plug flow photoreactor facilitates semi-heterogeneous dual nickel/carbon nitride photocatalytic C-N couplings

Carbon nitride materials have emerged as an efficient and sustainable class of heterogeneous photocatalysts, particularly when paired with nickel in dual catalytic cross-coupling reactions. Performing these transformations on larger scales using a continuous process is difficult due to the problems associated with handling solids in flow. By combining an oscillatory pump with a microstructured plug flow photoreactor, a stable suspension of the photocatalyst can be maintained, circumventing clogging of the reactor channels. Through careful tuning of the oscillator properties, the residence time distribution (RTD) was optimized, whilst maintaining a stable catalyst suspension. Short residence times (20 min) were achieved using optimized conditions and the recyclability of the photocatalyst was demonstrated over 10 cycles with no loss of activity. During a stable 4.5 hour scale-out demonstration, the model substrate could be isolated on 12 g scale (90% yield, 2.67 g h −1 ). Moreover, the method was applied for the gram scale synthesis of an intermediate of the active pharmaceutical ingredient tetracaine. Dual nickel/photocatalytic C-N couplings are performed with an organic heterogeneous photocatalyst, in an oscillatory plug flow reactor. Reaction was complete in 20 min residence time, enabling 2.7 g h −1 throughput and 10-fold catalyst recycling.