Organophosphorus compounds with P-stereogenic centers are valuable motifs in pharmaceuticals, agrochemicals, organocatalysts and ligands.^[1] Only a limited number of catalytic enantioselective approaches have been developed to access molecules with a P-stereogenic center.^[2] 

Chang et al. reported an Ir(III) catalyzed amidation of arylphosphine oxides that proceeds in modest enantioselectivities.^[3] We report that our recently developed chiral Cp^XIr(III) complex,^[4] in combination with a chiral carboxylic acid, provides a highly selective C-H amidation process. A very strong cooperative effect between the chiral Cp^XIr(III) complex and the carboxylic acid was discovered. This proved to be pivotal for high enantioselectivities and yields. 

[1] P. C. J. Kamer, P. W. N. M. van Leeuwen, Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis, John Wiley & Sons, Chichester, 2012.

[2] Y. Huang, Y. Li, P. H. Leung, T. Hayashi, J. Am. Chem. Soc. 2014, 136, 4865–4868.

[3] D. Gwon, S. Park, S. Chang, Tetrahedron 2015, 71, 4504–4511.

[4] M. Dieckmann, Y. Jang, N. Cramer, Angew. Chem. Int. Ed. 2015, 54, 12149–12152.