Hoye Thomas R, Hu Min
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
J Am Chem Soc. 2003 Aug 13;125(32):9576-7. doi: 10.1021/ja035579q.
A total synthesis of dactylolide (1) is described. The key feature involves the Ti(IV)-mediated coupling of structurally complex "Sharpless epoxides" and carboxylic acids in either an intramolecular (macrolactonization) or an intermolecular mode. Other notable aspects include a proton-catalyzed, cis-selective construction of the 4-methylenetetrahydropyran ring; a selective oxidation of an allylic alcohol in the presence of a 1,2-diol by an oxoammonium ion; an efficient ring-closing metathesis reaction of an in situ (bis-TMS) protected alpha,omega-diene-vic-diol; and an aluminum-mediated aza-aldol reaction of a primary amide to 1 to construct the acyclic carbinolamide in zampanolide.
本文描述了指状内酯（1）的全合成。关键特征包括在分子内（大环内酯化）或分子间模式下，由钛（IV）介导的结构复杂的“夏普莱斯环氧化合物”与羧酸的偶联。其他显著方面包括质子催化的4-亚甲基四氢吡喃环的顺式选择性构建；在1,2-二醇存在下，通过氧鎓离子对烯丙醇的选择性氧化；原位（双三甲基硅基）保护的α,ω-二烯-邻二醇的高效闭环复分解反应；以及铝介导的伯酰胺与1的氮杂羟醛反应，以构建赞帕诺内酯中的无环甲醇酰胺。
