Planar chiral ferrocenes are widely studied structures in asymmetric catalysis, materials science and medicinal chemistry. Although synthetic methods for 1,2-disubstituted planar chiral ferrocenes are well known, methods for the direct construction of 1,3-disubstituted planar chiral ferrocenes remain elusive. Here we report a modular platform for the construction of planar chirality in 1,3-disubstituted ferrocenes/ruthenocenes via an enantioselective relay remote C–H activation strategy. This method demonstrates a mechanism for remote enantiocontrol via enantiodetermining initial C‒H activation at the C2 position, enabled by a chiral mono-N-protected natural amino-acid ligand, and subsequent relay to the remote C3 position by a bridgehead-substituted norbornene mediator. A wide variety of 1,3-disubstituted planar chiral metallocenes are prepared with high enantioselectivity (96‒99% e.e.). The reaction shows good functional-group tolerance and high step-economy, and aryl iodides/bromides are compatible as coupling partners. The resulting metallocenes can be readily derivatized to yield planar chiral ligands and catalysts for asymmetric catalysis as well as building blocks for other applications.

平面手性二茂铁是不对称催化、材料科学和药物化学中广泛研究的结构。尽管 1,2-二取代平面手性二茂铁的合成方法众所周知，但直接构建 1,3-二取代平面手性二茂铁的方法仍然难以捉摸。在这里，我们报告了一个模块化平台，用于通过对映选择性中继远程 C-H 激活策略在 1,3-二取代二茂铁/茂钌中构建平面手性。该方法展示了一种通过对映体确定 C2 位置的初始 C-H 激活进行远程对映体控制的机制，由手性单-N启用-受保护的天然氨基酸配体，随后通过桥头取代的降冰片烯介体传递到远程 C3 位置。以高对映选择性 (96-99% ee) 制备了多种 1,3-二取代平面手性茂金属。该反应显示出良好的官能团耐受性和高步骤经济性，并且芳基碘化物/溴化物作为偶联伙伴是相容的。由此产生的茂金属可以很容易地衍生为平面手性配体和用于不对称催化的催化剂以及用于其他应用的结构单元。