Continuous flow photo-thiol-ene reactions on cinchona alkaloids with a variety of organic thiols have been developed to deliver a series of unprecedented architectures. A self-optimizing flow photochemical reactor was deployed...

This work demonstrates the in‐line monitoring of a flow photochemical reaction using 1D and ultrafast 2D NMR methods at high magnetic field. The reaction mixture exiting the flow reactor is flown through the NMR spectrometer and directly analyzed. In the case of simple substrates, suitable information can be obtained through 1D 1H spectra, but for molecules of higher complexity the use of 2D experiments is key to address signal overlaps and assignment issues. Here we show the usefulness of ultrafast 2D COSY experiments acquired in 70 s or less, for the in‐line monitoring of photochemical reactions, and the possibility to obtain reliable quantitative information. This is a powerful framework to, for example, efficiently screen reaction conditions.