Herein, we report a regio-and stereoselective distal C–H functionalization protocol for ferrocenes, leading to the synthesis of planar chiral ferrocene-1,3-derivatives by a Catellani-type reaction. The successful Pd(II)/norbornene catalyst combination can reach the inaccessible reaction site of ferrocene and accomplishes the selective C(3)-arylation of ferrocenyl methylamine. The ligand-controlled synergistic Pd/norbornene metal–organic cooperative catalysis under aerobic conditions successfully provides an array of ferrocene-1,3-derivatives in moderate-to-good yields with good enantio- and diastereoselectivities. A unique class of ferrocene 1,3-ligands, including PPFA-like and pincer type ligands bearing central and planar chirality, has been successfully synthesized by following this synthetic methodology.

中文翻译：

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通过钯/降冰片烯协同催化对映选择性合成二茂 1,3-衍生物


在此，我们报道了二茂铁的区域和立体选择性远端 C-H 功能化方案，导致通过 Catellani 型反应合成平面手性二元二茂铁-1,3-衍生物。成功的 Pd（II）/降冰片烯催化剂组合可以到达二茂铁难以接近的反应位点，并完成二茂铁甲胺的选择性 C（3）-芳基化。在好氧条件下，配体控制的协同 Pd/降冰片烯金属-有机协同催化成功地提供了一系列二茂铁-1,3-衍生物，产率中等到良好，具有良好的对映和非对映选择性。遵循这种合成方法已成功合成了一类独特的二茂铁 1,3-配体，包括具有中心和平面手性的 PPFA 样配体和钳型配体。