Merino Pedro, Jimenez Pablo, Tejero Tomas
Laboratorio de Sintesis Asimetrica, Departamento de Quimica Organica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza, CSIC, E-50009 Zaragoza, Aragon, Spain.
J Org Chem. 2006 Jun 9;71(12):4685-8. doi: 10.1021/jo060465t.
The addition of a 2-silyloxy silylketene acetal to N-benzyl-2,3-O-isopropylidene-D-glyceraldehyde nitrone (Mannich-type reaction) can be stereocontrolled to give 2S,3S,4S and 2R,3R,4S adducts as major compounds, depending on whether the reaction is activated with zinc(II) triflate or tin(IV) chloride, respectively. The corresponding major adducts were used for preparing diastereomeric polyhydroxy-beta-aminoesters that were further converted into suitable orthogonally protected enantiomeric D- and L-erythro-sphingosines.
将2-硅氧基硅基乙烯酮缩醛添加到N-苄基-2,3-O-异亚丙基-D-甘油醛硝酮上(曼尼希型反应),根据反应分别用三氟甲磺酸锌(II)或四氯化锡活化,可实现立体控制,以2S,3S,4S和2R,3R,4S加合物作为主要化合物生成。相应的主要加合物用于制备非对映体多羟基-β-氨基酯,这些酯进一步转化为合适的正交保护对映体D-和L-赤藓糖神经鞘氨醇。