新型手性联萘修饰的金属卟啉的合成及催化烯烃环氧化作用

Synthesis of Novel Chiral Binaphthyl Compounds Modified Metalloporphyrins and Their Catalysis of Asymmetric Epoxidation of Olefins

合成了系列新型手性联萘化合物1～9和具有不同手性空腔的新型刚性联萘卟啉14～17.利用元素分析、UV-Vis,MS(HRMS),IR,1HNMR,13CNMR及旋光分析等手段进行了表征.由于卟啉配合物的手性空腔大小不同,不同金属(Fe,Zn,Mn)的取代反应表现出很大的差异.用1HNMR对其中代表性的联萘化合物6,8和手性卟啉14,16的结构特点进行了讨论.以亚碘酰苯为氧源,将手性铁卟啉15和17应用于苯乙烯衍生物环氧化反应,催化结果表明该类催化剂具有高的对映选择性和催化稳定性,拥有合适手性空腔尺寸的15对苯乙烯的对映选择性为e.e.93%,转化率96%,在转化数为10000时仍保持了e.e.82%值.

A new series of chiral binaphthyl compounds 1～9 and rigid chiral porphyrins 14～17 with similar chiral auxiliaries but with different dimensions of chiral pockets were synthesized and characterized by elemental analysis, UV-Vis, MS, IR, ^1H NMR and 13C NMR. The structural traits of new compounds and porphyrins were discussed by ^1H NMR. The iron（Ⅲ） porphyrins 15 and 17 were used as catalysts in asymmetric styrene derivative epoxidation. Both catalysts exhibit remarkable chemoselectivity and enantioselectivity using iodosobenzene as oxidant, 93% e.e. and 96% yield have been obtained and 82% e.e. has been maintained while up to 10000 turnovers catalyzed by 15 for styrene at room temperature. The dimension of chiral pockets is the most important and sensitive factors for the efficient chiral catalytic epoxidation. The different metaUafion methods for the free bases 14 and 16 with iron, zinc and manganese support the deduction.