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A Pd-catalyzed highly regio- and stereoselective hydrocyanation was developed, providing a novel approach to the stereodivergent synthesis of β-cyano-substituted acrylates in good yields with a wide substrate scope. The judicious selection of ligands was crucial for elegant control over the stereodivergence. Furthermore, the success of the E-hydrocyanation hinges on the right matching of Pd and L1, which not only ensured the catalytic activity but also prevented the formation of α-cyanation products.

The first catalytic enantioselective hydrocyanation of allenes catalyzed by a (R,R)-Ph-BPE–Ni(0) complex catalyst has been accomplished. Numerous optically active allylic nitriles were obtained in good yield with excellent enantioselectivities (up to 98% ee).

Copper-catalyzed oxidative intramolecular cyclization of o-alkylated anilines via cleavage of C(sp3)–H and N–H bonds for the production of indolines is described. This approach provides a straightforward strategy for the synthesis of nitrogen-containing heterocyclic compounds through the functionalization of unactivated C(sp3)–H bonds with high site selectivity. The present catalytic system shows high preference for functionalization of unactivated C(sp3)–H bonds over C(sp2)–H bonds, leading to C–N bond formation.

Nickel-catalyzed aqueous cyanation of allylic alcohols is herein described. This catalytic protocol provided environmentally friendly and operationally simple access to a variety of allylic nitriles in good yields. For chiral allylic alcohols, the reaction gave chiral allylic nitriles with a high degree of chiral inversion. The accelerated release of cyanide in H2O was crucial for the success of this reaction.

Herein reported is a nickel-catalyzed isomerization/allylic cyanation of alkenyl alcohols, which complements current methods for the allylic substitution reactions. The specific diphosphite ligand and methanol as the solvent are crucial for the success for this transformation. A gram-scale regioconvergent experiment and formal synthesis of quebrachamine demonstrate the high potential of this methodology.