Phosphonite Ligand Design for Nickel‐Catalyzed 2‐Methyl‐3‐butenenitrile Isomerization and Styrene Hydrocyanation

The synthesis of a series of novel chelating bisphosphonite ligands with a bridged dihydroanthracene scaffold is described. First‐generation derivatives showed a strong tendency for the formation of catalytically inactive Ni0 bis‐chelate complexes. The solid state structures of these complexes allowed the design of tailor‐made second‐generation ligands for nickel‐catalyzed 2‐methyl‐3‐butenenitrile isomerization with exceptionally high activity. The second‐generation catalyst also showed good catalytic performance in the hydrocyanation of styrene.