Alphonse France-Aimée, Yudin Andrei K
Davenport Research Laboratories, Department of Chemistry, The University of Toronto, Toronto, Ontario, Canada M5S 3H6.
J Am Chem Soc. 2006 Sep 13;128(36):11754-5. doi: 10.1021/ja0632557.
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.
铑（I）催化的N-烯丙基氮丙啶异构化反应能以优异的产率和高立体选择性得到可分离的Z-烯胺。阳离子型[Rh（BINAP）（COD）]OTf和RhH（CO）（PPh3）3对Z-异构体具有相同的选择性。而其他N-烯丙基胺则生成热力学上更稳定的E-异构体，未观察到这种选择性。这些意外结果表明异构化机制可能偏离了普遍接受的机理。初步结果表明，Z-烯胺与DMAD发生环加成反应，形成高度张力的N-环丁烯基氮丙啶。
