Synthesis of Chirality Controlled Optically active Ferrocenes and Their Application to Catalytic Asymmetric Synthesis

邻-TMS封闭的(二甲氨基)苯甲基二茂铁与tBuLi发生了意外的1，5-二锂化合反应，1，5-二锂化二茂铁被卤素捕获，然后TMS基团被脱除，以合理的产率得到1，5-二卤代二茂铁。1，5-二碘二茂铁通过二硫化和Ph_2PCl捕集的顺序转化为TaNiaphos配体。1，5-二锂硫代二茂铁在Fe(Acac)_3的作用下发生分子内偶联反应得到甲氧基-1，5-二膦，其苯环被tBuLi邻位锂化合，然后用Ph_2PCl捕获生成相应的氨基膦。以Fe(Acac)_3为催化剂，通过1，5-二锂基膦对苯二甲酸的分子内偶联反应合成了环戊二烯基上含膦基团的氨基膦，并将其应用于基准钯配合物催化的1，3-二苯基-2-丙烯基乙酸酯的烯丙烷基化和胺化反应，得到了较好的结果(产率高，对映选择性高，ee高达96%ee)。

The 1, 5-dilithiation of o-TMS blocked (dimethylamino) phenylmethylferrocene with tBuLi unexpectedly occurred and the 1, 5-dilithiated ferrocene was trapped by halogen followed by removal of the TMS group to give the 1, 5-dihaloferrocene in a reasonable yield. The 1, 5-diiodoferrocene was converted into Taniaphos ligand by the sequencial of dilithiation and trapping with Ph_2PCl. The methoxy 1, 5-diphosphane was obtained by the inversive substitution of the dimethylamino group by NaOMe and subsequent dilithiation and trapping with Ph_2PC 1. The homoannularly bridged ferrocene was prepared by the intramolecular coupling of the 1, 5-dilithioferrocene mediated by Fe(acac)_3. Its benzene ring underwent ortho-lithiation by tBuLi, and subsequent trapping with Ph_2PCl produced the corresponding aminophosphine. The aminophosphine which has the phosphinyl group on the cyclopentadienyl group was prepared by intramolecular coupling of 1, 5-dilithiated Ph-PPFA mediated by Fe(acac)_3. The new N, P-ligands were applied to the benchmark palladium complex-catalyzed allylic alkylation and amination of the 1, 3-diphenyl-2-propenyl acetate and was found to give good results (good yields with high enantioselectivities, up to 96% ee).