Catalytic Photochemical Deracemization via Short-Lived Intermediates

Upon irradiation in the presence of a suitable chiral catalyst, racemic compound mixtures can be converted into enantiomerically pure compounds with the same constitution. The process is called photochemical deracemization and involves the formation of short-lived intermediates. By opening different reaction channels for the forward reaction to the intermediate and for the re-constitution of the chiral molecule, the entropically disfavored process becomes feasible. Since the discovery of the first photochemical deracemization in 2018, the field has been growing rapidly. This review comprehensively covers the research performed in the area and discusses current developments. It is subdivided according to the mode of action and the respective substrate classes. The focus of this review is on the scope of the individual reactions and on a discussion of the mechanistic details underlying the presented reaction. Photochemical deracemization offers a unique opportunity to directly obtain enantiopure compounds from their racemates. Short-lived intermediates play a key role in the enantioselectivity-determining step. The review covers comprehensively the research performed in the area and discusses current developments.image