Catalytic asymmetric rearrangement of allylic N-aryl trifluoroacetimidates. A useful method for transforming prochiral allylic alcohols to chiral allylic amines.
[reaction: see text] A useful method for the conversion of prochiral allylic alcohols to chiral allylic amines of high enantiopurity is reported. N-(4-Methoxyphenyl)trifluoroacetimidates are excellent substrates for the palladium(II)-catalyzed allylic imidate rearrangement as the allylic trifluoroacetamide products can be deprotected in two steps to provide chiral nonracemic allylic amines. Di-mu-chlorobis[(eta(5)-(S)-(pR)-2-(2'-(4'-isopropyl))oxazolinylcyclopentadienyl,1-C,3'-N))(eta(4)-tetraphenylcyclobutadiene)cobalt]dipalladium (6a, COP-Cl) is a superior catalyst because it does not require activation with silver salts and provides rearranged allylic trifluoroacetamides in good yields and high enantiomeric purities.
Overman
Larry E
LE
Department of Chemistry, University of California, Irvine, 516 Rowland Hall, Irvine, California 92697-2025, USA. leoverma@uci.edu
Owen
Carolyn E
CE
Pavan
Mary M
MM
Richards
Christopher J
CJ
D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D007096:Imidoesters / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D012834:Silver / Q000737:chemistry; D013237:Stereoisomerism
D000438:Alcohols; D000498:Allyl Compounds; D000588:Amines; D007096:Imidoesters; D007202:Indicators and Reagents; D012834:Silver