Naphthol radical couplings determine structural features and enantiomeric excess of dalesconols in Daldinia eschscholzii
Naphthol radical couplings determine structural features and enantiomeric excess of dalesconols in Daldinia eschscholzii
复制标题
萘酚自由基偶联决定 Daldinia eschscholzii 中 dalesconol 的结构特征和对映体过量
DOI：
10.1038/ncomms2031
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发表时间：
2012-09-01
影响因子：
16.6
通讯作者：
Tan, Ren Xiang
中科院分区：
文献类型：
--
作者：
Fang, Wei;Ji, Shen;Tan, Ren Xiang
了解生物体中简单分子是如何拼凑在一起的，可能有助于生物技术操作和复杂天然产物的合成方法。螳螂相关真菌艾氏炭层壳（Daldinia eschscholzii）IFB-TL 01产生异常结构的免疫抑制剂（±）-达来司康醇A和B，沿着它们的同源物（±）-达来司康醇C，（-）-对映体过量。在这里，我们报告的这些结构和立体化学特性的dalesconols A-C的混杂和atropselective耦合的自由基衍生自1，3，6，8-四羟基萘，1，3，8-三羟基萘和1，8-二羟基萘的结果。观察到的（-）-对映体过量被发现依赖于萘酚二聚体中间体，这是漆酶的配体的特定构象的优势。
Understanding how simple molecules are pieced together in organisms may aid biotechnological manipulation and synthetic approaches to complex natural products. The mantis-associated fungus Daldinia eschscholzii IFB-TL01 produces the unusually structured immunosuppressants (±)-dalesconols A and B, along with their congener (±)-dalesconol C, with the (-)-enantiomers in excess. Here we report that these structural and stereochemical peculiarities of dalesconols A-C are a result of promiscuous and atropselective couplings of radicals derived from 1,3,6,8-tetrahydroxynaphthalene, 1,3,8-trihydroxynaphthalene and 1,8-dihydroxynaphthalene. The observed (-)-enantiomeric excess is found to depend on the dominance of particular conformers of naphthol dimer intermediates, which are ligands of laccase.