Yan Bingli, Spilling Christopher D
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, 8001 Natural Bridge Road, St. Louis, Missouri 63121, USA.
J Org Chem. 2004 Apr 16;69(8):2859-62. doi: 10.1021/jo035795h.
A combination of cross-metathesis and malonate addition was applied to a formal synthesis of the mammalian lignan enterolactone 5. The cross-metathesis of alkene 6 and phosphonate 3a gave the substituted allylic phosphonate 3d. The palladium-catalyzed addition of malonate 10d to the allylic phosphonate 3d was stereospecific and highly regioselective and yielded the vinyl phosphonate 11d. The vinyl phosphonate 11d was converted in two steps into the lactone 14, a known intermediate in the synthesis of enterolactone 5.
交叉复分解反应和丙二酸加成反应相结合被应用于哺乳动物木脂素肠内酯5的形式合成。烯烃6和膦酸酯3a的交叉复分解反应得到取代烯丙基膦酸酯3d。钯催化丙二酸酯10d加成到烯丙基膦酸酯3d上具有立体专一性和高区域选择性，生成乙烯基膦酸酯11d。乙烯基膦酸酯11d经两步转化为内酯14，这是肠内酯5合成中的一个已知中间体。
