trans-1,2-Cyclohexanediamine, -diether, and -amino ether were compared as chiral inducers in the asymmetric intramolecular carbolithiation of olefinic aryllithiums. Switching from diamine to ethereal ligands inverts the sense of asymmetric induction. This reversal of stereoselectivity was investigated through density functional theory calculations. High enantioselectivities observed with diether and amino ether ligands arise from favorable weak interactions between the ligand and the substrate. The relative efficiency of the three ligands and sense of stereoinduction for the most efficient diether and amino ether ligands prove to be foreseeable by modeling the reaction with the parent achiral 1,2-bidentate additives and comparing the diastereomeric transition states stemming from the two half-chair conformations of their lithium chelate.

中文翻译：

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对1,2-二胺，-二醚和-氨基醚手性配体介导的碳锂化的计算洞察：对映诱导逆转的情况。

反式在烯属芳基锂的不对称分子内碳锂化反应中，将-1，2-环己二胺，-二醚和-氨基醚作为手性诱导剂进行了比较。从二胺配体到醚配体会改变不对称感应的感觉。通过密度泛函理论计算研究了这种立体选择性的逆转。用二醚和氨基醚配体观察到的高对映选择性是由于配体与底物之间有利的弱相互作用引起的。通过模拟与母体非手性1,2-二齿添加剂的反应并比较源自两个半-锂螯合物的椅子构象。