d‐Fructose Based Spiro‐Fused PHOX Ligands: Palladium Complexes and Application in Catalysis.

Phosphinooxazoline (PHOX) ligands are an important class of ligands in asymmetric catalysis. Recently we reported on the synthesis of d‐fructose based spiro‐fused PHOX ligands. Here, we now present the application of these ligands in asymmetric alkylation. In addition, we prepared palladium complexes of our previous spiro‐PHOX ligands and characterized them by X‐ray crystallography. With the knowledge of the molecular structure of these spiro‐PHOX palladium complexes we prepared two "improved" d‐fructose based spiro‐fused PHOX ligands the application of which in asymmetric alkylation resulted in high enantioselectivities (er up to 93:7) in a broad substrate range. [ABSTRACT FROM AUTHOR]