手性3-取代联二萘酚衍生物的合成及在不对称环氧化中的应用

Synthesis of 3-Substituted BINOL derivatives and application in asymmetric epoxidation reaction

目的:研究α,β不饱和酮的不对称环氧化反应。方法:利用手性的3-取代联二萘酚和Fe3+、La3+、Al3+的配和物诱导不对称环氧化反应。结果:成功合成了三个3取代联二萘酚衍生物,并将其运用于不对称环氧化反应。手性La3+配合物催化的环氧化反应,取得88%的产率以及46%对映异构体过量;手性Fe3+和Al3+配合物体系,环氧化产率较高,产物为消旋体。结论:手性的3-羟甲基联二萘酚镧配合物能够催化α,β不饱和酮的不对称环氧化反应并获得较高产率和中等的对映选择性。对该不对称环氧化反应的研究,为合成光活性环氧化物类药物中间体提供了新方法。

Objective： To study the asymmetric epoxidation of α,β-unsaturated ketone with BINOL derivative as catalyst. Method： The chiral 3-substitued-BINOL derivative ligands were first synthesized ,and then coordinated with Fe3＋, La3＋or Al3＋to catalyze the asymmetric epoxidation of chalcone. Results： The 3-substituted BINOL derivatives （4~5） were successfully synthesized and applied in the asymmetric epoxidation of chalcone. The optical active epoxide was obtained in high yield （88%） and moderate ee value （46%） with 3-hydroxyl-methylnaphthol/La3＋ as catalyst,while poor enantioselectivity was observed when the 3-hydroxylmethylnaphthol/Fe3＋or 3-hydroxylmethylnaphthol/Al3＋complex was used. Conclusion： The chiral 3-hydroxylmethylnaphthol/La3＋complex is able to catalyze the asymmetric epoxidation of chalcone in high yield and moderate enantioselectivity , which pvovides a new approach to the construction of optical epoxide intermediate in the synthesis of material and medicine.