( S )‐6‐Bromo‐BINOL‐based phosphoramidite ligand with C 1 symmetry for enantioselective hydrogenation and allylic substitution

( S )‐6‐Br‐BINOL‐derived phosphoramidite, a s imple monodentate ligand with a stereogenic center at the phosphorus atom, was synthesized for the first time. This stereoselector generated a high level of enantioselectivity (80–95% ee ) in the rhodium‐catalyzed hydrogenation of α‐dehydrocarboxylic acid esters and was also successfully employed in the asymmetric palladium‐catalyzed allylic substitution of ( E )‐1,3‐diphenylallyl acetate. The optical yield also showed significant dependence with reaction type: up to 70% ee for allylic amination, up to 75% ee for allylic sulfonylation, and up to 90% ee for allylic alkylation. Chirality, 2010. © 2010 Wiley‐Liss, Inc.