Department of Chemistry, Analytical and Biological Chemistry Research Facility, University College Cork, Cork, Ireland.
J Org Chem. 2012 Feb 17;77(4):2035-40. doi: 10.1021/jo202499j. Epub 2012 Feb 7.
The asymmetric synthesis of cis-7-methoxycalamenene 1 has been accomplished using the intramolecular Buchner reaction of α-diazoketone 7 as the key step in the synthetic route. Upon reduction of the equilibrating azulenone structure 8, the resulting azulenol 9 rearranges to dihydronaphthalene 10 containing the 6,6-membered bicyclic ring system characteristic of 1, by means of an acid-catalyzed aromatization process. Transformation of 10 to 1 is accomplished through a three-step reaction sequence.
顺式-7-甲氧基姜黄烯 1 的不对称合成已通过α-重氮酮 7 的分子内 Buchner 反应完成，该反应是合成路线中的关键步骤。在平衡的薁酮结构 8 还原后，所得薁醇 9 通过酸催化的芳构化过程重排为含有 6,6-元双环体系的二氢萘 10，这是 1 的特征。通过三步反应序列将 10 转化为 1。
