Palladium/BINAP(S)-catalyzed asymmetric allylic amination.
The enantioselective allylic amination of acyclic allylic carbonates catalyzed by a palladium/(S)-BINAP(S) system was investigated. Amination of several substrates proceeded with high ee. Crotyl carbonates show an unusually high regioselectivity for the branched isomer. The use of (S)-TolBINAP(S) and (S)-3,5-xylyl-BINAP(S) as ligands was found to increase the enantioselectivity of the aminations. A P,S binding mode of the BINAP(S) ligand was found in an X-ray crystallographic study. [reaction: see text]
Faller
J W
JW
Department of Chemistry, Yale University, New Haven, CT 06520, USA. jack.faller@yale.edu
Wilt
Jeremy C
JC