Starting from (R)-N,N-dimethyl-1-ferrocenylethylamine, a diastereoselective ortho-lithiation procedure and a stereoconvergent intramolecular hydrophosphination gave access to P-chiral ferrocenephospholanes. These mono- or bidentate ligands were converted to the corresponding rhodium and iridium complexes, including a chiral version of Crabtree's catalyst, and tested in the asymmetric hydrogenation of functionalized and unfunctionalized olefins. A significant reactivity difference between the rhodium-1,5-cyclooctadiene and the rhodium-norbornadiene complex was observed during catalyst activation.

…P-chiral phospholanes can be readily prepared from (R)-N,N-dimethyl-1-ferrocenylethylamine by means of an ortho-lithiation procedure followed by a stereoconvergent hydrophosphination reaction. These mono-or bidentate ligands were converted to the corresponding Rh and Ir complexes, including a chiral version of Crabtree's catalyst, and tested in the asymmetric hydrogenation of olefins. For more details see the Full Paper by A. Pfaltz, B. Pugin et al. on page 12993 ff. Inside CoverBjçrn Gschwend, Benoît Pugin*, Andreas Bertogg, and Andreas Pfaltz* Enantiomerically pure… …P-chiral phospholanes can be readily prepared from (R)-N,N-dimethyl-1-ferrocenylethylamine by means of an ortho-lithiation procedure followed by a stereoconvergent hydrophosphination reaction. These mono-or bidentate ligands were converted to the corresponding Rh and Ir complexes, including a chiral version of Crabtree's catalyst, and tested in the asymmetric hydrogenation of olefins. For more details see the Full Paper by A. Pfaltz, B. Pugin et al. on page 12993 ff.