Smith Amos B, Mesaros Eugen F, Meyer Emmanuel A
Department of Chemistry, Monell Chemical Senses Center, and Laboratory for Research on the Structure of Matter, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
J Am Chem Soc. 2006 Apr 19;128(15):5292-9. doi: 10.1021/ja060369+.
A convergent stereocontrolled total synthesis of (-)-kendomycin (1) has been achieved. The synthesis proceeds with a longest linear sequence of 21 steps, beginning with commercially available 2,4-dimethoxy-3-methylbenzaldehyde (12). Highlights of the synthesis include an effective Petasis-Ferrier union/rearrangement tactic to construct the sterically encumbered tetrahydropyran ring, a ring-closing metathesis to generate the C(4a-13-20a) macrocycle, an effective epoxidation/deoxygenation sequence to isomerize the C(13,14) olefin, and a biomimetic quinone-methide-lactol assembly to complete the synthesis.
已实现（-）-肯多霉素（1）的汇聚式立体控制全合成。该合成以21步的最长线性序列进行，从市售的2,4-二甲氧基-3-甲基苯甲醛（12）开始。合成的亮点包括用于构建空间位阻四氢吡喃环的有效Petasis-Ferrier偶联/重排策略、用于生成C（4a-13-20a）大环的闭环复分解反应、用于使C（13,14）烯烃异构化的有效环氧化/脱氧序列，以及用于完成合成的仿生醌甲基化物-内酯组装。
