The iron-catalyzed directed ortho-functionalization of arenes developed to an important method in the field of C–H activation. On the other hand, the iron-catalyzed ortho-functionalization of ferrocenes bearing ortho-directing groups (ODGs) has scarcely been investigated. Herein we present the iron-catalyzed ortho-alkylation and -arylation of ODG-substituted ferrocenes bearing a bidentate ODG with the formation of racemic 1,2-disubstituted ferrocenes in up to 94% yield. The approach toward an enantioselective iron-catalyzed C–H activation resulted in an ortho-phenylation with a promising enantiomeric excess of 46%. The first iron-catalyzed diastereoselective ortho-methylation gave an excellent diastereomeric excess of ≥99%.

中文翻译：

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定向铁催化的邻烷基化和芳基化：面向1,2-二取代的平面手性二茂铁衍生物的立体选择性催化合成

铁催化的芳烃直接邻位官能化发展成为C–H活化领域的重要方法。另一方面，几乎没有研究过带有邻位导向基团（ODG）的二茂铁的铁催化邻位官能化。本文中，我们提出了铁催化的带有双齿ODG的ODG-取代的二茂铁的ODG-取代的二茂铁的邻位烷基化和芳基化，形成外消旋的1,2-二取代的二茂铁，产率高达94％。进行对映选择性铁催化的C–H活化的方法导致了邻苯基化，对映体过量的可能性达到46％。第一个铁催化非对映选择性邻苯二甲酸酯-甲基化产生出色的非对映异构体过量，≥99％。