探索了N,O-缩醛7 C-2位的不对称烯丙基化的条件,建立了路易斯酸催化条件下高选择性烯丙基化方法(产率73%,dr 94∶6).并以此为关键反应,合成了制备(-)-Epiquinamide(1)的关键中间体21.作为延续性工作,建立了一条由(2S,3S)和(2S,3R)-9差向异构体混合物制备光学纯(+)-Febrifugine(3)的方法.从而开发了一条以廉价谷氨酸为原料制备克级常山碱的可能途径.
Lewis acid catalyzed asymmetric allylation ofN, O-acetal 7 with allyltrimethylsilane was developed for the synthe- sis of compounds 9, 10 and 16 with high disasterselectivities. A key middle compound 21 for synthesis of (--)-epiquinamide (1) was easily prepared from allylation product 16. In continuation of our work, a convenient method for synthesis of (+)-febrifugine (3) was also described from the mixture of (2S,3S) and (2S,3R)-9. Therefore, a possible approach for gram scale preparation of (+)-febrifugine (3) from glutamic acid was achieved.