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Rhodium(III)‐Catalyzed Enantiotopic C−H Activation Enables Access to P ‐Chiral Cyclic Phosphinamides
Author(s) -
Sun Yang,
Cramer Nicolai
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201606637
Subject(s) - stereocenter , rhodium , enantioselective synthesis , chemistry , cyclopentadienyl complex , catalysis , ligand (biochemistry) , stereochemistry , phosphorus , combinatorial chemistry , transition metal , medicinal chemistry , organic chemistry , receptor , biochemistry
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.