Total Synthesis of Brasilicardins A and C
Total Synthesis of Brasilicardins A and C
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DOI：
10.1021/acs.orglett.7b02728
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发表时间：
2017-10-20
期刊：
影响因子：
5.2
通讯作者：
Hashimoto, Shunichi
中科院分区：
文献类型：
--
作者：
Anada, Masahiro;Hanari, Taiki;Hashimoto, Shunichi
报道了具有独特免疫抑制活性的新型二萜类糖胺杂化代谢物巴西木素A和C的首次全合成。关键步骤是Diels-Alder/还原角甲基化序列，利用跨融合双环α -氰- α - β -烯酮作为前体，构建8,10-二甲基反式/syn/反式过氢苯基骨架。其他值得注意的特征包括反选择性醛醇反应，C2醇的立体控制糖基化，以及不损害这些敏感分子的一锅两步全局去保护序列。
The first total synthesis of brasilicardins A and C, novel diterpenoid saccharide amine acid hybrid metabolites with unique immunosuppressive activity, is described. The key step is a Diels-Alder/reductive angular methylation sequence capitalizing on a trans-fused bicyclic alpha-cyano-alpha,beta-enone as its precursor to construct the 8,10-dimethyltrans/syn/trans,perhydrophenanthierie skeleton. Other notable features include an,anti selective aldol reaction, a stereocontrolled glycosylation of a C2 alcohol, and a one-pot, two-step global deprotection sequence that did not damage these sensitive molecules.