Crimmins Michael T, Christie Hamish S, Long Alan, Chaudhary Kleem
Venable and Kenan Laboratories of Chemistry, Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Org Lett. 2009 Feb 19;11(4):831-4. doi: 10.1021/ol802829n.
A highly convergent, enantioselective total synthesis of the potent antitumor agent apoptolidin A has been completed. The key transformations include highly selective glycosylations to attach the C27 disaccharide and the C9 6'-deoxy-l-glucose, a cross-metathesis to incorporate the C1-C10 trienoate unit, and a Yamaguchi macrolactonization to complete the macrocycle. Twelve stereocenters in the polypropionate segments and sugar units were established through diastereoselective chlorotitanium enolate aldol reactions.
高效抗肿瘤药物凋亡诱导素A的高收敛性对映选择性全合成已完成。关键转化步骤包括用于连接C27二糖和C9 6'-脱氧-L-葡萄糖的高选择性糖基化反应、用于引入C1-C10三烯酸酯单元的交叉复分解反应以及用于完成大环结构的山口大环内酯化反应。通过非对映选择性氯钛酸烯醇酯羟醛缩合反应构建了聚丙酸酯片段和糖单元中的12个立体中心。
