ENANTIOSELECTIVE TOTAL SYNTHESIS OF (+)-12,13-EPOXYTRICHOTHEC-9-ENE AND ITS ANTIPODE
ENANTIOSELECTIVE TOTAL SYNTHESIS OF (+)-12,13-EPOXYTRICHOTHEC-9-ENE AND ITS ANTIPODE
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DOI：
10.1021/ja00222a036
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发表时间：
1988-07-06
影响因子：
15
通讯作者：
PAUKSTELIS, JV
中科院分区：
文献类型：
--
作者：
HUA, DH;VENKATARAMAN, S;PAUKSTELIS, JV
研究了不同环烯丙基亚砜衍生物与2-环戊烯酮衍生物阴离子的1，4-加成反应。3-环戊烯酮C-3位的甲基取代阻碍了1，4-加成反应。然而，活化的烯酮，2-（甲氧羰基）-3-甲基-2-环烯酮（4），提供了优异的化学和光学产率的1，4-加合物。（+）-12，13-环氧十六碳-9-烯[（+）1]及其对映体（. sbd.）-以（S）-（-）-4-甲基-2-环己烯酮为起始原料，经11步反应，对映选择性地合成了化合物1。
The 1,4-addition reactions of the anions derived from various cyclic allylic sulfoxides and 2-cyclopentenones were examined. Methyl substitution at C-3 of 3-cyclopentenones hinders the 1,4-addition. The activated enone, 2-(methoxycarbonyl)-3-methyl-2-cyclopenetenone (4), however, afforded excellent chemical and optical yields of the 1,4-adducts. (+)-12,13-Epoxytrichothec-9-ene [(+)1] and its antipode (.sbd.)-1 were enantioselectively synthesized from (S)-(-)-4-methyl-2-cyclohexenone in 11 steps.