用于构建双环[2.2.2]二氮杂辛烷结构的分子间狄尔斯-阿尔德环加成反应：短杆菌酰胺B和前马氏分支酰胺的形式合成。
Intermolecular Diels-Alder Cycloaddition for the Construction of Bicyclo[2.2.2]diazaoctane Structures: Formal Synthesis of Brevianamide B and Premalbrancheamide.
作者信息
Robins Jacob G, Kim Kyu J, Chinn Alex J, Woo John S, Scheerer Jonathan R
机构信息
Department of Chemistry, The College of William & Mary , P.O. Box 8795, Williamsburg, Virginia 23187, United States.
出版信息
J Org Chem. 2016 Mar 18;81(6):2293-301. doi: 10.1021/acs.joc.5b02744. Epub 2016 Feb 26.
Abstract
A stereoselective intermolecular Diels-Alder cycloaddition of an intermediate pyrazinone with both achiral and chiral acrylate-derived dienophiles provides rapid access to the bicyclo[2.2.2]diazaoctane core shared among several prenylated indole alkaloids. The product derived from cycloaddition with 2-nitroacrylate required an additional five to six synthetic operations to intercept established precursors to premalbrancheamide and brevianamide B. The chemistry detailed in this manuscript constitutes a formal total synthesis (12 steps each) of these [2.2.2]diazabicyclic natural products from proline methyl ester.
摘要
中间体吡嗪酮与非手性和手性丙烯酸酯衍生的亲双烯体进行立体选择性分子间狄尔斯-阿尔德环加成反应，能够快速构建几种异戊烯基化吲哚生物碱共有的双环[2.2.2]二氮杂辛烷核心。与2-硝基丙烯酸酯环加成得到的产物需要额外进行五到六步合成操作，才能得到已确定的前马氏支链酰胺和短杆菌肽B的前体。本论文详细阐述的化学合成方法实现了以脯氨酸甲酯为原料，通过形式上的全合成（各12步）得到这些[2.2.2]二氮杂双环天然产物。
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