Continuous microflow visible-light photocatalytic N-formylation of piperidine and its kinetic study

N-formylation of amines, a class of synthetically important reactions, is typically conducted using metal catalysts that are relatively expensive or not readily available and usually needs harsh conditions to increase the reaction efficiency. Here, an efficient continuous microflow strategy was developed for the gas-liquid visible-light photocatalytic N-formylation of piperidine, which achieved a reaction yield of 82.97% and a selectivity of >99% at 12 min using cheap organic dye photocatalyst under mild reaction conditions. The influence of essential parameters, including light intensity, temperature and equivalents of the gas, additive and photocatalyst, on the reaction yield was systematically studied. Furthermore, kinetic investigations were conducted, exhibiting the dependence of reaction rate and equilibrium yield of N-formylpiperidine on light intensity, temperature and photocatalyst equivalent. The microflow photocatalytic approach established in this work, which realized a markedly higher space-time yield than the conventional batch method (37.9 vs. 0.212 mmol h⁻¹ L⁻¹), paves the way for the continuous, green and efficient synthesis of N-formamides.