Sun, YangCramer, Nicolai2017-05-012017-05-012017-05-01201710.1002/anie.201606637https://infoscience.epfl.ch/handle/20.500.14299/136656WOS:000394861200059Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition-metal as well as organocatalysts. A direct catalytic enantioselective method for the synthesis of P-chiral compounds from easily accessible diaryl phosphinamides is presented. The use of rhodium(III) complexes equipped with a suitable atropochiral cyclopentadienyl ligand is shown to enable an enantiodetermining C-H activation step. Upon trapping with alkynes, a broad variety of cyclic phosphinamides with a stereogenic phosphorus(V) atom are formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically to P-chiral phosphorus(III) compounds.asymmetric catalysisC-H activationchiral Cp ligandsP-chiralityrhodiumtext::journal::journal article::research article