Studies of the Enantiocontrolled Synthesis of the C(10)–C(25) Subunit of Amphidinolide C
Studies of the Enantiocontrolled Synthesis of the C(10)–C(25) Subunit of Amphidinolide C
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Amphidinolide C C(10)-C(25) 亚基的对映体控制合成研究
DOI：
10.1021/acs.orglett.0c01177
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发表时间：
2020
期刊：
影响因子：
5.2
通讯作者：
Rodríguez-Reyes, David
中科院分区：
文献类型：
--
作者：
Williams, David R.;De, Ramkrishna;Fultz, Micheal W.;Fischer, Derek A.;Morales-Ramos, Ángel;Rodríguez-Reyes, David
通过立体控制合成了28个双内酯C(1)的C(10)-C(25)组分。二硫杂环戊烷组分21与非外消旋双(环氧化物)19直接反应得到官能化的2，5-反式二取代四氢呋喃22。丙烯酰化对于形成所需的C(12)-C(13)反立体化学具有高度的非对映选择性，生成的末端烷基25用于区域选择性的硅锡化反应。说明了一种连续取代三取代烯烃的锡基和硅基取代基以生成(E)-烯基碘28的一般策略。
A stereocontrolled synthesis of28, the C(10)–C(25) component of amphidinolide C (1), has been efficiently achieved. Reaction of the dithiane component21with nonracemic bis(epoxide)19directly affords functionalized 2,5-trans-disubstituted tetrahydrofuran22. Propargylation is highly diastereoselective for the formation of the desired C(12)–C(13)antistereochemistry, and the resulting terminal alkyne25is utilized for a regioselectivesyn-silylstannylation. A general strategy is illustrated for sequential replacement of stannyl and silyl substituents of the trisubstituted alkene to yield (E)-alkenyl iodide28.