Iridium(I)-catalyzed asymmetric intermolecular hydroarylation of norbornene with benzamide

Iridium(I)-catalyzed asymmetric intermolecular hydroarylation of norbornene with benzamide
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DOI:
10.1007/s007060070014
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发表时间:
2000-12-01
影响因子:
1.8
通讯作者:
Togni, A
Togni, A
中科院分区:
化学4区
文献类型:
--
作者:
Aufdenblatten, R;Diezi, S;Togni, A

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以氯桥双核Ir(I)配合物[IrCl(PP)](2)(PP=(R)-(6,6 '-二甲基联苯-2,2'-二基)-1,1 '-双-(二苯基膦)和(R)-1-((S)-2-(二苯基膦基二茂铁基))-乙基二环己基膦)为原料,合成并表征了一类新的含手性双膦的双氯桥Ir(I)配合物[IrCp(PP)].这些新的配合物是苯甲酰胺与异丙基苯直接氢芳基化反应的合适预催化剂。通过使用1摩尔%铱,形成对映体过量高达94%的2-(外-降冰片基)-苯甲酰胺,尽管产率低。
Starting from the dinuclear chloro-bridged Ir(I) complexes [IrCl(PP)](2) (PP=(R)-(6,6'-dimethylbiphenyl-2,2'-diyl)- 1, 1'-bis-(diphenylphosphine),and (R)-1-((S)-2-(diphenlyphosphino-ferrocenyl))-ethyldicyclohexyl-phosphine),a new class of cyclopentadienyl Ir(I) complexes containing a chiral bisphosphine ([IrCp(PP)]) was prepared and characterized. These new complexes are suited precatalysts for the direct hydroarylation of norbornene with benzamide. 2-(exo-Norbornyl)-benzamide is formed with an enantiomeric excess of up to 94% by the use of 1 mol% iridium, albeit in low yield.