ASYMMETRIC TOTAL SYNTHESIS OF ATISINE VIA INTRAMOLECULAR DOUBLE MICHAEL REACTION
ASYMMETRIC TOTAL SYNTHESIS OF ATISINE VIA INTRAMOLECULAR DOUBLE MICHAEL REACTION
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DOI：
10.1021/ja00159a042
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发表时间：
1990-01-31
影响因子：
15
通讯作者：
KABUTO, C
中科院分区：
文献类型：
--
作者：
IHARA, M;SUZUKI, M;KABUTO, C
从环己酮-2，6-二甲酸二甲酯（6）合成了天然存在的对映体形式的阿替辛（1）的桥接五环中间体2。该合成由以下关键步骤组成：（1）通过双曼尼希反应形成氮杂双环[3.3.1]壬烷，（2）通过脂肪酶催化的酰化进行对映选择性转化，（3）在BF 3存在下的立体选择性硼氢化。Et 2 O;（4）通过分子内双Michael反应构建双环[2.2.2]辛烷环体系。
The bridged, pentacyclic intermediate 2 for atisine (1) was synthesized in a naturally occurring enantiomeric form from dimethyl cyclohexanone-2,6-dicarboxylate (6). The synthesis is composed for the following key steps: (1) formation of the azabicyclo[3.3.1]nonane by a double Mannich reaction, (2) enantioselective conversion by a lipase-catalyzed acylation, (3) stereoselective hydroboration in the presence of BF3 .cntdot. Et2O, and (4) construction of the bicyclo[2.2.2]octane ring system by an intramolecular double Michael reaction.