Enantioselective total synthesis of parnafungin A1 and 10a-epi-hirtusneanine.
Enantioselective total synthesis of parnafungin A1 and 10a-epi-hirtusneanine.
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DOI：
10.1039/d1sc02919c
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发表时间：
2021-08-04
期刊：
影响因子：
8.4
通讯作者：
Tang W
中科院分区：
文献类型：
--
作者：
Sun J;Gu W;Yang H;Tang W
本文首次对映选择性地合成了异二聚体联芳基抗真菌天然产物parnafungin A1和配合物联芳基四羟基蒽酮10a-外延-喜图宁氨酸，通过苯并恶硼罗勒交叉偶联构建了它们的位阻联芳基核。除了强大的Suzuki-Miyaura交叉偶联外，parnafungin A1的合成还具有高度非对映选择性的oxa-Michael加成以构建四羟基蒽酮骨架，以及有效的zn介导的还原环化- mitsunobu序列以提供异恶唑烷酮结构。全合成10a-外延-黑图英氨酸的关键创新包括在四羟基蒽酮骨架上使用DTBS保护来控制官能团，立体选择性甲基化，利用氧化/ Evans-Saksena还原完全逆转c5 -羟基的立体化学，以及从相同的手性中间体制备两种复杂的四羟基蒽酮单体的策略。首先，利用交叉偶联策略构建了它们的位阻联芳基核，完成了异二聚联芳基抗真菌天然产物parnafungin A1和10a-epi-hirtusneanine的对映选择性全合成。
The first and enantioselective total synthesis of the heterodimeric biaryl antifungal natural product parnafungin A1 as well as complex biaryl tetrahydroxanthone 10a-epi-hirtusneanine is accomplished, by employing cross-coupling through the benzoxaborole strategy to construct their sterically hindered biaryl cores. Besides the powerful Suzuki–Miyaura cross-coupling, the synthesis of parnafungin A1 also features a highly diastereoselective oxa-Michael addition to construct a tetrahydroxanthone skeleton, and an effective Zn-mediated reductive cyclization-Mitsunobu sequence to furnish the isoxazolidinone structure. Key innovations in total synthesis of 10a-epi-hirtusneanine include the employment of DTBS protection for functional group manipulation on the tetrahydroxanthone skeleton, stereoselective methylations, and complete reversal of the stereochemistry of the C5-hydroxy group using oxidation/Evans–Saksena reduction, as well as the strategy of preparing both complex tetrahydroxanthone monomers from the same chiral intermediate 25. The first, enantioselective total synthesis of the heterodimeric biaryl antifungal natural product parnafungin A1 as well as 10a-epi-hirtusneanine is accomplished, using a cross-coupling strategy to construct their sterically hindered biaryl cores.
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