A small library of chiral imidate-ferrocenylphosphane ligands was efficiently synthesized (8 examples) and evaluated in the iridium(I)-catalyzed hydrogenation of unfunctionalized and poorly functionalized olefins. These catalysts perform very well in a range of examples (yields and ee's up to 100%).

Chiral imidate–phosphanes were developed as a new type of N,P ligands. These ligands are easily accessible through a one‐step procedure starting from a commercially available chiral aminophosphane and an imidate precursor. Excellent performance of the catalyst system was observed with various carbon nucleophiles in the Pd0‐catalyzed asymmetric allylic alkylation (up to 99 % yield and >99 % ee). Moreover, good to excellent enantioselectivities could also be obtained in the allylic alkylation of more difficult linear unhindered substrates and cyclic substrates, demonstrating that this new catalyst system has a broad substrate scope.

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