Rhodium(III)-Catalyzed Enantiotopic C-H Activation Enables Access to P-Chiral Cyclic Phosphinamides.
Title | Rhodium(III)-Catalyzed Enantiotopic C-H Activation Enables Access to P-Chiral Cyclic Phosphinamides. |
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Authors | Sun, Y.; Cramer, N. |
Journal | Angew Chem Int Ed Engl |
DOI | 10.1002/anie.201606637 |
Abstract |
Compounds 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. |