Total Synthesis of the Reported Structure of Stresgenin B Enabled by the Diastereoselective Cyanation of an Oxocarbenium
Total Synthesis of the Reported Structure of Stresgenin B Enabled by the Diastereoselective Cyanation of an Oxocarbenium
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DOI：
10.1021/acs.orglett.8b03219
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发表时间：
2018-12-21
期刊：
影响因子：
5.2
通讯作者：
Koide, Kazunori
中科院分区：
文献类型：
--
作者：
Chan, Wei Chuen;Koide, Kazunori
我们报道了第一次报道的热休克蛋白表达抑制因子Stresgenin B的结构的全合成。合成的特征是(1)氧碳正离子中间体的非对映选择性氰化反应，(2)钯催化的不稳定腈的水合反应，以及(3)金催化的Meyer-Schuster重排或Ce介导的Peterson烯化反应提供外环α，β-不饱和酯。我们的综合努力使我们得出结论，应激素B的结构需要修改。
We report the first total synthesis of the reported structure of the heat shock protein expression inhibitor stresgenin B. The synthesis features (1) diastereoselective cyanation of an oxocarbenium intermediate en route to the synthetically challenging alpha-amido dioxolane, (2) Pd-catalyzed hydration of an unstable nitrile, and (3) late-stage Au-catalyzed Meyer-Schuster rearrangement or Ce-mediated Peterson olefination to furnish the exocyclic alpha,beta-unsaturated ester. Our synthetic endeavors allowed us to conclude that the structure of stresgenin B requires revision.