Wenderski Todd A, Huang Shenlin, Pettus Thomas R R
Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, California 93106, USA.
J Org Chem. 2009 Jun 5;74(11):4104-9. doi: 10.1021/jo900401k.
Enantioselective syntheses of all of the named chiral members of the cleroindicin family (C-F) are reported. This effort demonstrates the synthetic utility of a 2,4-dihydroxybenzaldehyde as a starting material for natural product synthesis through the use sequential o-quinone methide chemistry and diastereoselective dearomatization. Natural cleroindicin F was shown to be nearly racemic, and an optically pure synthetic sample of cleroindicin F was found to racemize under slightly basic conditions. All other natural chiral cleroindicins are shown to be partially racemic.
本文报道了对clerodindicin家族中所有指定手性成员（C - F）的对映选择性合成。这项工作证明了2,4 - 二羟基苯甲醛作为天然产物合成起始原料的合成效用，其通过连续使用邻醌甲基化物化学和非对映选择性去芳构化反应来实现。研究表明天然的clerodindicin F几乎是外消旋的，并且发现clerodindicin F的光学纯合成样品在弱碱性条件下会发生外消旋化。所有其他天然手性clerodindicins均显示为部分外消旋。
