Rhodium-catalyzed stereoselective formation of Z-enamines from allylaziridines.
Rhodium (I)-catalyzed isomerization of N-allylaziridines affords isolable Z-enamines in excellent yields and with high stereoselectivity. Cationic [Rh(BINAP)(COD)]OTf and RhH(CO)(PPh3)3 follow the same selectivity toward the Z-isomers. This selectivity is not observed with other N-allylamines which give the thermodynamically more stable E-isomers. These unexpected results suggest a possible deviation from the commonly accepted mechanism of isomerization. Preliminary results show that the Z-enamines undergo cycloaddition with DMAD to form highly strained N-cyclobutenyl aziridines.
Alphonse
France-Aimée
FA
Davenport Research Laboratories, Department of Chemistry, The University of Toronto, Toronto, Ontario, Canada M5S 3H6.
Yudin
Andrei K
AK
D000498:Allyl Compounds / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis*; D001388:Aziridines / Q000737:chemistry*; D002384:Catalysis; D012238:Rhodium; D013237:Stereoisomerism
D000498:Allyl Compounds; D000588:Amines; D001388:Aziridines; D012238:Rhodium