摘要
具有四个新手性中心的螺环 /环丙烷类化合物 4在丙酮 12 %HCl溶液中 5 0℃下发生双手性辅基 -双水解转换反应 ,得到了手性环丙烷 /双半缩醛类化合物 ,螺 [1 溴 4 羟基 5 氧杂 6 氧代双环 [3.1.0 ]己烷 2 ,2′ ( 3′ 亲核氧基 4′ 羟基丁内酯 ) ] ( 5 ) ,化学产率 6 5 %～ 79%,光学纯度ee≥ 98%.通过元素分析 ,[α] 2 0D ,UV ,IR ,1HNMR ,13 CNMR ,MS以及X射线四圆衍射测定 ,确认了它们的化学结构、立体化学和绝对构型 .该双半缩醛类化合物的合成方法学研究可为官能团的转换 ,为某些复杂结构的手性化合物提供新的合成方法和途径 .
The functionalized spiro-cyclopropane derivatives containing four stereogenic centers 4 were undergone stereoselective double hydrolytic transformation of the auxiliary groups in the presence of acetone/12% HCl to afford the crude products 5. After separation though column chromatography and recrystallization, the pure chiral cyclopropane/bis-hemiacetal derivatives, spiro-[1-bromo-4-hydroxy-5-oxa-6-oxo-bicyclo-[3.1.0]-hexane-2, 2'-( 3'-nucleophilic group-4'-hydroxy-butyrolactone) 1 (5), were obtained in 65% similar to 79% yields with ee greater than or equal to 98%. The novel chiral compounds 5a similar to 5e were identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H-1 NMR, C-13 NMR, MS, elementary analysis and X-ray crystallography analysis.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2003年第1期76-80,共5页
Chinese Journal of Organic Chemistry
基金
国家自然科学基金 (No.2 9672 0 0 4 )资助项目
