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

用tBuLi意外地发生o-TMS封闭的（二甲基氨基）苯基甲基二茂铁的1，5-硫代化，并且1，5-硫代化的二茂铁被卤素捕获，随后除去TMS基团，以合理的产率得到1，5-二卤代二茂铁。以1，5-二碘二茂铁为配体，经缩合、Ph_2PCl捕集等步骤，合成了谷硫磷配体。用NaOMe对二甲氨基进行反式取代，然后进行双硫代，再用Ph_2PC1捕集，得到甲氧基1，5-二膦。以Fe（acac）_3为催化剂，通过分子内偶联1，5-二硫代二茂铁，制备了均环桥联二茂铁.其苯环被tBuLi邻位锂化，随后被Ph_2PCl捕获生成相应的氨基膦。以Fe（acac）_3为催化剂，通过分子内偶联1，5-二硫代Ph-PPFA，合成了氨基膦。新的N，P-配体被应用于基准钯络合物催化的烯丙基烷基化和胺化的1，3-二苯基-2-丙烯基乙酸酯，并发现得到良好的结果（良好的产率和高的对映选择性，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).