手性杯[4]丝氨酸衍生物的合成及其催化性能

Synthesis and Catalytic Properties of Chiral Calix[4]serine Derivative

以对叔丁基苯酚为原料,经环化缩合、脱叔丁基、酚羟基醚化、甲酰化和氧化反应制得5-羧基-25,26,27,28-四正丙基杯[4]芳烃(5);5与O-苄基-N-苄氧羰基丝氨酸反应制得5-(O-丝氨酸)-25,26,27,28-四正丙基杯[4]甲酸酯(7),其结构经~1H NMR,^(13)C NMR和MS(ESI)表征。研究了溶剂和水的用量对7催化性能的影响。结果表明:水为溶剂,其用量为10 eq.时,收率和非对映选择性分别为95%和3∶97 dr;当水的用量为30 eq.时,收率和非对映选择性分别为93%和98∶2 dr。

5-Carboxyl-25,26,27,28-tetra（1-propyloxy） calix[4]arene（5） was synthesized by serial reactions of cyclizative condensation,elimination of tert-butyl,etherification of phenolic hydroxyl,formylation and oxidation reaction from para tert-butyl phenol. 5-（O-serine）-25,26,27,28-tetra（1-propyloxy） calix[4]arene formate（7） was prepared by reaction of 5 with O-benzyl-N-[（benzyloxy）carbonyl]serinate. The structure was characterized by^1H NMR,^13C NMR,and MS（ESI）. Catalytic properties of 7 were investigated by screening different solvents and loading of water. The results illustrated that 95% yield and 3 ∶ 97 dr were observed when the reaction was performed in 10 eq. water while 93% yield and 98 ∶ 2 dr were obtained by using 30 eq. water.