Regiodivergent Catalysis: A Powerful Tool for Selective Catalysis.

"Regiodivergent catalysis" is discussed as a class of highly selective reactions of chiral substrates in racemic or enantiomerically enriched form using one or both enantiomers of a catalyst. The key point of the reactions is the highly regioselective formation of products that are constitutional isomers. The selectivity is mediated by different interactions of the enantiomerically pure catalysts with both enantiomers of the substrate. Ideally, for racemic substrates, the reactions result in highly efficient parallel resolutions and for enantiomerically pure substrates, in highly regioselective reactions for each enantiomer of the catalyst. "Regiodivergent catalysis" is highly interesting for diversity-oriented synthesis (DOS) because it provides branching points for the generation of functional and structural diversity.