Nichols Alexander L, Zhang Patricia, Martin Stephen F
Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165.
Tetrahedron. 2012 Sep 16;68(37):7591-7597. doi: 10.1016/j.tet.2012.05.094.
The rapid synthesis of 1,4-dioxygenated xanthones and related natural products employing the Moore rearrangement as a key transformation has been developed. The approach features an acetylide stitching step to unite a substituted squaric acid with a protected hydroxy benzaldehyde derivative to provide a key intermediate that undergoes facile Moore rearrangement to deliver a hydroxymethyl aryl quinone. Subsequent oxidation, hydroxy group deprotection and cyclization then affords highly functionalized xanthones. The utility of the approach was demonstrated by its application to a concise and efficient synthesis of the naturally-occurring xanthone 1. The structure of a natural product that had been named dulcisxanthone C was also corrected to that of the xanthone 1.
已开发出以摩尔重排为关键转化步骤的1,4 - 二氧代呫吨酮及相关天然产物的快速合成方法。该方法的特点是有一个乙炔化拼接步骤，将取代的方酸与受保护的羟基苯甲醛衍生物结合，以提供一个关键中间体，该中间体经容易的摩尔重排生成羟甲基芳基醌。随后的氧化、羟基脱保护和环化反应得到高度官能化的呫吨酮。该方法的实用性通过将其应用于天然存在的呫吨酮1的简洁高效合成得到了证明。一种曾被命名为dulcisxanthone C的天然产物的结构也被修正为呫吨酮1的结构。
