Synthesis and Application of Planar Chiral Cyclic (Amino)(ferrocenyl)carbene Ligands Bearing FeCp* Group
Synthesis and Application of Planar Chiral Cyclic (Amino)(ferrocenyl)carbene Ligands Bearing FeCp* Group
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含FeCp*基团的平面手性环状(氨基)(二茂铁基)卡宾配体的合成及应用
DOI：
10.1021/acs.organomet.9b00171
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Yoshida Kazuhiro
中科院分区：
文献类型：
--
作者：
Yasue Risa;Yoshida Kazuhiro
新的含Cp*基团的环（氨基）（二茂铁基）碳（CAFeC）配体已被开发出来作为其原型Cp版本的修饰。新碳烯的生成是通过捕集实验间接证实的，在捕集实验中，碳烯前体在碱的存在下与硫或[IrCl(cod)]2反应。通过测定由[IrCl(cod)(CAFeC)]合成的Ir二羰基配合物[IrCl(CO)2(CAFeC)]的Tolman电子参数（TEP）来评价新CAFeC的电子性能。结果表明，新cafec的供体强度非常高，可与环（氨基）（烷基）碳烯（CAACs）相媲美。在以cafec为手性配体的环-磺酰亚胺不对称转移加氢反应中，证实了将Cp改变为Cp*基团的空间效应对其对映选择性的显著影响。
New cyclic (amino)(ferrocenyl)carbene (CAFeC) ligands containing the Cp* group have been developed as a modification of their prototype Cp version. The generation of the new carbenes was indirectly confirmed by trapping experiments in which a carbene precursor was reacted with sulfur or [IrCl(cod)]2in the presence of a base. The electronic properties of the new CAFeCs were evaluated by determining the Tolman electronic parameter (TEP) of the Ir dicarbonyl complex [IrCl(CO)2(CAFeC)] that was synthesized via [IrCl(cod)(CAFeC)]. It was revealed that the donor strengths of the new CAFeCs were very high and comparable to those of cyclic (amino)(alkyl)carbenes (CAACs). The influence of the steric effect on the enantioselectivity by changing Cp to the Cp* group of CAFeCs was confirmed to be significant in an Ir-catalyzed asymmetric transfer hydrogenation of cyclicN-sulfonylimine where CAFeCs were used as chiral ligands.