克癌菌素发色团：其假定结构的合成及立体化学修正的证据
Kedarcidin chromophore: synthesis of its proposed structure and evidence for a stereochemical revision.
作者信息
Ren Feng, Hogan Philip C, Anderson Alan J, Myers Andrew G
机构信息
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
出版信息
J Am Chem Soc. 2007 May 2;129(17):5381-3. doi: 10.1021/ja071205b. Epub 2007 Apr 7.
Abstract
A convergent, enantioselective synthesis of the proposed structure of kedarcidin chromophore () is described. The route is 24 steps in the longest linear sequence (beginning with the commercial reagent 2,3--isopropylidene-d-erythronolactone) with an average yield of 75% per step (overall yield: 0.1%). Our H NMR data for do not coincide with the data reported for kedarcidin chromophore. We have re-analyzed the original data and here propose a stereochemical revision at position C10, the site of attachment of the l-mycarose carbohydrate residue to the chromophore core (structure ).
摘要
描述了一种对所提出的克氏菌素发色团（）结构进行的汇聚式对映选择性合成。该路线在最长线性序列中为24步（从市售试剂2,3 - 异丙叉基 - d - 赤藓糖内酯开始），每步平均产率为75%（总产率：0.1%）。我们得到的的核磁共振氢谱数据与报道的克氏菌素发色团数据不一致。我们重新分析了原始数据，在此提出在C10位置进行立体化学修正，C10位置是L - 蜜二糖碳水化合物残基连接到发色团核心的位点（结构）。
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本文引用的文献
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Highly selective synthesis of (E)-3-methyl-1-trialkylsilyl-3-en-1-ynes via trans-selective alkynylation catalyzed by Cl2Pd(DPEphos) and stereospecific methylation with methylzincs catalyzed by Pd(tBu3P)2.通过Cl2Pd(DPEphos)催化的反式选择性炔基化反应以及Pd(tBu3P)2催化的甲基锌立体定向甲基化反应，高度选择性合成(E)-3-甲基-1-三烷基甲硅烷基-3-烯-1-炔。
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Enantioselective synthesis of kedarcidin chromophore aglycon in differentially protected form.
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Evidence for facile atropisomerism and simple (non-nucleophilic) biradical-forming cycloaromatization within kedarcidin chromophore aglycon.
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A Direct and Efficient alpha-Selective Glycosylation Protocol for the Kedarcidin Sugar, L-Mycarose: AgPF(6) as a Remarkable Activator of 2-Deoxythioglycosides This work was supported by CREST, and fellowships (to M.J.L. and F.Y.) from the Japanese Society for the Promotion of Science are gratefully acknowledged.
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