Seo Seung-Yong, Jung Jae-Kyung, Paek Seung-Mann, Lee Yong-Sil, Kim Seok-Ho, Lee Kwang-Ok, Suh Young-Ger
College of Pharmacy, Seoul National University, Seoul 151-742, Korea.
Org Lett. 2004 Feb 5;6(3):429-32. doi: 10.1021/ol0363366.
[reaction: see text] The asymmetric total synthesis of bacillariolide III has been achieved via 15 linear steps in 14.6% overall yield. The key feature of this synthetic route involves the highly stereoselective construction of the vinyl-substituted bicyclic lactone by an intramolecular Pd(0)-catalyzed allylic alkylation and its facile conversion to the hydroxy bicyclic lactone skeleton of bacillariolide III, induced by stereoselective vinylcerium addition to the aldehyde. In addition, the (Z)-pentenoic acid was efficiently introduced by the internal hydroxy group tethered ring-closing metathesis (RCM).
[反应：见正文] 通过15步线性反应实现了杆菌内酯III的不对称全合成，总收率为14.6%。该合成路线的关键特征包括通过分子内钯(0)催化的烯丙基烷基化高度立体选择性地构建乙烯基取代的双环内酯，以及通过立体选择性乙烯基铈加成到醛上，将其轻松转化为杆菌内酯III的羟基双环内酯骨架。此外，通过内部羟基连接的闭环复分解反应（RCM）有效地引入了(Z)-戊烯酸。
