"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.

We describe a regiodivergent epoxide opening (REO) featuring a catalyst-controlled synthesis of enantiomerically and diastereomerically highly enriched or pure syn- and anti- 1,3- and 1,4-difunctionalized building blocks from a common epoxide precursor. The REO is attractive for natural product synthesis and as a branching reaction for diversity-oriented synthesis with epoxides.

A novel highly regioselective, fluoride-catalyzed hydrosilylation of β-hydroxy epoxides has been developed. The reaction is modular and applicable to the synthesis of a broad range of 1,4-diols. Fluoride is crucial for two reasons: First, it promotes the formation of a silyl ether (which contains a Si-H bond) and, second, it enables ring opening by an intramolecular S(N)2 reaction through activation of the silane. The reaction can be performed under air.

We describe a regiodivergent synthesis of pseudo‐C2‐symmetrical and pseudo‐meso bis‐indoline scaffolds from norbornadiene and substituted o‐iodo‐anilines. The Pd(0)/Josiphos system enables the highly regioselective catalyst controlled carboaminations required for the two step synthesis of the scaffolds.

We describe a regiodivergent epoxide opening (REO) featuring a catalyst-controlled synthesis of enantiomerically and diastereomerically highly enriched or pure syn-and anti-1,3-and 1,4-difunctionalized building blocks from a common epoxide precursor. The REO is attractive for natural product synthesis and as a branching reaction for diversity-oriented synthesis with epoxides. Angewandte Chemie CommunicationsScheme 2. Performance of the REO in the reaction of ricinolate-derived diastereomeric mixtures of epoxides. Regioisomeric ratios: from isolated yields.Scheme 3. Synthetic approach to the REO substrates. Angewandte Chemie Communications