CSIR-Indian Institute of Chemical Technology, Hyderabad 500607, India.
J Org Chem. 2011 Aug 5;76(15):6331-7. doi: 10.1021/jo200396q. Epub 2011 Jul 8.
Enantioselective total synthesis of mupirocin H is accomplished starting from D-glucose featuring strategic application of D-glucose derived chirality, diastereoselective Still-Barrish hydroboration, and further elaboration of carbon chain to furnish a phenyltetrazolyl sulfone intermediate, which on coupling with (2S,3S)-2-methyl-3-(triisopropylsilyloxy)butanal under Julia-Kocienski olefination conditions gave an advanced E-olefinic intermediate selectively. The E-olefin was transformed to the 4-hydroxynitrile, a prefinal substrate, which on acid-catalyzed oxidative lactonization furnished the target molecule mupirocin H in 19 steps from known compound 6 (longest linear sequence) with an overall yield of 4.96%.
从 D-葡萄糖出发，通过策略性地利用 D-葡萄糖衍生的手性、立体选择性 Still-Barrish 硼氢化反应，以及进一步拓展碳链来合成苯并四唑基砜中间体，实现了莫匹罗星 H 的对映选择性全合成。该中间体与（2S,3S）-2-甲基-3-（三异丙基甲硅烷基氧基）丁醛在 Julia-Kocienski 烯烃化条件下偶联，选择性地得到了高级 E-烯烃中间体。E-烯烃转化为 4-羟基腈，这是一个预终产物，在酸催化氧化内酯化条件下，从已知化合物 6（最长线性序列）出发，经过 19 步反应，以 4.96%的总收率得到目标分子莫匹罗星 H。
