多氧取代环己基甲醇苯甲酸酯的合成及其表征

Synthesis and Characterization of Polyoxygenated Cyclohexyl-methanol Benzoic Acid Ester

以莽草酸为原料,经酯化、丙酮叉保护顺式邻二羟基、叔丁基二甲基硅烷保护羟基、还原、羟基酯化、最后双羟基化反应,得到多氧取代环己基甲醇苯甲酸酯(1),总产率为84.1%,其结构经IR、1H NMR和HR MS确证。对双羟基化反应的条件进行了探索,优化条件为:反应时间为15h,溶剂为THF∶H2O=1∶1(V∶V),配料比为n[(3R,4R,5R)-5-叔丁基二甲基硅氧基-3,4-(丙酮叉二氧)-环己基-1-烯烃-1-甲醇苯甲酸酯(5)]∶n(N-甲基吗啉氮氧化物)∶n(OsO4)∶n(手性配体)=100∶150∶0.5∶1,产率为90.6%,e.e.值为75.1%。

Polyoxygenated cyclohexyl-methanol benzoic acid ester was synthesized from shikimic acid by esterification, protection of diol and hydroxy respectively, reduction, esterification and dihydroxylation with an overall yield of 84. 1%, and its structure was confirmed by IR, ^1H NMR and HR MS. The conditions for dihydroxylation were studied. The optimized conditions were as follows： the reaction time was 15 h, THF ： H2O=1：1（V ： V） was used as solvent, and the ratio of n（5） ： n（NMMNO） ： n（OsO4） ：n（chiral ligand）= 100 ：150 ： 0.5 ： 1. The maximum yield of dihydroxylation under these conditions could reach 90.6% and the e.e. value was 75.1%.