Department of Chemistry, University of Texas at Austin Austin, Texas 78712, United States.
Org Lett. 2017 Dec 15;19(24):6634-6637. doi: 10.1021/acs.orglett.7b03351. Epub 2017 Nov 23.
The C(1)-C(13) fragment of the antimitotic marine macrolide leiodermatolide is prepared in seven steps via hydrogenative and transfer-hydrogenative reductive C-C couplings. A hydrogen-mediated reductive coupling of acetylene with a Roche-type aldehyde is used to construct C(7)-C(13). A 2-propanol-mediated reductive coupling of allyl acetate with (E)-2-methylbut-2-enal at a low loading of iridium (1 mol %) is used to construct C(1)-C(6), which is converted to an allylsilane using Oestereich's copper-catalyzed allylic substitution of Si-Zn reagents. The union of the C(1)-C(6) and C(7)-C(13) fragments is achieved via stereoselective Sakurai allylation.
通过氢化和转移氢化还原 C-C 偶联反应，以七步反应制备抗有丝分裂海洋大环内酯类药物 leiodermatolide 的 C(1)-C(13) 片段。通过乙炔与 Roche 型醛的氢介导还原偶联反应构建 C(7)-C(13)。在铱（1 摩尔%）的低负载下，使用 2-丙醇介导的烯丙基乙酸酯与（E）-2-甲基-2-丁烯醛的还原偶联反应构建 C(1)-C(6)，然后使用 Oestereich 的铜催化 Si-Zn 试剂的烯丙基取代反应将其转化为烯丙基硅烷。通过立体选择性 Sakurai 烯丙基化反应实现 C(1)-C(6)和 C(7)-C(13)片段的连接。
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