Catalytic Asymmetric Synthesis of Chiral Transition-Metal Complexes by the Use of Modern Organic Transformation

1，2-二烯丙基二茂铁衍生物在钼催化的不对称闭环歧化反应(ARCM)中进行动力学拆分，得到相应的铁(II)衍生物，产率高，对映体选择性高。同样地，(1，2，3-三烯丙基)茂金属在ARCM中的去对称化反应得到了相应的(1，4-二氢荧基)茂金属衍生物，具有较高的对映选择性，Cs对称的茂锆烯可以转化为相应的C3桥联的平面手性安莎-茂锆烯。得到的平面手性安莎-茂锆络合物可作为不对称碳金属化反应的催化剂。钼催化的ARCM具有良好的对映体选择性，实现了外消旋平手性(芳烃)铬配合物的动力学拆分。由此得到的光学活性(溴芳烃)铬络合物是合成各种平面手性(芳烃)铬络合物的良好前驱体。

Kinetic resolution of 1,2-diallylferrocene derivatives by Mo-catalyzed asymmetric ring-closing metathesis (ARCM) gave the corresponding (4,7-dihydroindenyl)iron(II) derivatives in good yields with high enantioselectivity. In the same way, desymmetrization of (1,2,3-triallylindenyl)-metallocenes by ARCM provided the corresponding (1,4-dihydrofluorenyl)-metallocene derivatives in high ee's.The Cs-symmetric zirconocenes could be converted to the corresponding C3-bridged planar-chiral ansa-zirconocenes by ARCM with high enantioselectivity. The obtained planar-chiral ansa-zirconocene complexes could be applicable to the asymmetric carbometallation reaction as catalysts.Kinetic resolution of the racemic planar-chiral (arene)chromium complexes was realized by Mo-catalyzed ARCM with excellent enantioselectivity. The optically active (bromoarene)chromium complex thus obtained is an excellent precursor to various planar-chiral (arene)chromium complexes.