Asymmetric Synthesis of Griffipavixanthone Employing a Chiral Phosphoric Acid-Catalyzed Cycloaddition.
Asymmetric Synthesis of Griffipavixanthone Employing a Chiral Phosphoric Acid-Catalyzed Cycloaddition.
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DOI：
10.1021/jacs.8b12520
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发表时间：
2018-11
影响因子：
15
通讯作者：
Michael J Smith;Kyle D Reichl;Randolph A Escobar;Thomas J Heavey;D. Coker;S. Schaus;J. Porco
中科院分区：
文献类型：
--
作者：
Michael J Smith;Kyle D Reichl;Randolph A Escobar;Thomas J Heavey;D. Coker;S. Schaus;J. Porco
报道了具有生物活性的山酮二聚体griffipavixanthone的不对称合成及其绝对立体化学测定。天然产物的合成是通过使用手性磷酸催化剂对醌的二聚化来完成的，以提供具有优异的非映体和对映体选择性的受保护前体。机械研究，包括使用平行回火的手性离子对的无偏计算研究，进行了以探索不对称感应模式。
Asymmetric synthesis of the biologically active xanthone dimer griffipavixanthone is reported along with its absolute stereochemistry determination. Synthesis of the natural product is accomplished via dimerization of a p-quinone methide using a chiral phosphoric acid catalyst to afford a protected precursor in excellent diastereo- and enantioselectivity. Mechanistic studies, including an unbiased computational investigation of chiral ion-pairs using parallel tempering, were performed in order to probe the mode of asymmetric induction.