R* = (−)-menthyl; Ln = Sm, Y), and [Me2Si(η5-Me4C5)(CpR*)]SmN(TMS)2 (Cp = η5-H3C5; R* = (−)-menthyl) mediate asymmetric intramolecular hydroamination/cyclization of amines bearing internal olefins and afford chiral 2-substituted piperidine and pyrrolidine in enantioselectivities as high as 84:16 er at 60 °C. The substrate of the structure NH2CH2CMe2CH2CHCH(CH2)2CHCH2 is regiospecifically bicyclized
本文报道
金属有机催化的分子内加
氢胺化/胺-拴系的未活化的1,2-二取代的烯烃,得到使用的类型的配位不饱和复合物相应的单-和二取代的
吡咯烷和
哌啶环化(η 5 -Me 5 Ç 5)2 LnCH(TMS)2(Ln为La,Sm或),[我2的Si(η 5 -Me 4 ç 5)2 ] SmCH(TMS)2,和[我2的Si(η 5 -Me 4 ç 5)(吨BuN)] LnE(TMS)2(Ln = Sm,Y,Yb,Lu; E = N,CH)作为预催化剂。[我2的Si(η 5 -Me 4 Ç 5)(吨BUN)] LNE(TMS)2所介导的分子内加
氢胺化/的空间要求的
氨基烯烃,得到在高非对映选择性取代的
吡咯烷环化(反式/顺式= 16/1)且产量高到极好。另外,手性Ç 1个的类型[我的-对称
金属有机催化剂2的Si(OHF)(CPR *)] LNN(TMS)2(OHF =η 5 -octahydrofluorenyl;