Shimizu Ken-ichi, Tomita Mina, Fuhshuku Ken-ichi, Sugai Takeshi, Shoji Mitsuru
Department of Pharmaceutical Science, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan.
Nat Prod Commun. 2013 Jul;8(7):897-901.
A formal synthesis of (+)-madindoline A was achieved. The Sunazuka's key intermediate, (4R,5S)-(-)-3-butyl-4-(tert-butyldimethylsiloxy)-5-methoxycarbonyl-2,5-dimethyl-2-cyclopentenone, was synthesized from easily available (2S,3S)-3-acetoxy-2-ethenyl-2-methylcyclopentanone. The starting material was reliably supplied by a chemo-enzymatic procedure in enantiomerically pure form. The synthesis was performed by straightforward transformations involving enone formation and regioselective introduction of the two alkyl side chains.
实现了（+）-马吲哚啉A的形式合成。从容易获得的（2S，3S）-3-乙酰氧基-2-乙烯基-2-甲基环戊酮合成了砂冢的关键中间体（4R，5S）-（-）-3-丁基-4-（叔丁基二甲基硅氧基）-5-甲氧基羰基-2，5-二甲基-2-环戊烯酮。起始原料通过化学酶法以对映体纯的形式可靠地提供。该合成通过涉及烯酮形成和两个烷基侧链的区域选择性引入的直接转化来进行。
