Enantioselective Rhodium‐Catalyzed Coupling of Arylboronic Acids, 1,3‐Enynes,and Imines by Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

A chiral rhodium complex catalyzes the highly enantioselective coupling of arylboronic acids, 1,3‐enynes, and imines to give homoallylic sulfamates. The key step is the generation of allylrhodium(I) species by alkenyl‐to‐allyl 1,4‐rhodium(I) migration.     

Rhodium(III)‐Catalyzed Enantiotopic C−H Activation Enables Access to P‐Chiral Cyclic Phosphinamides

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.