Department of Chemistry, The College of William & Mary, P.O. Box 8795, Williamsburg, Virginia 23187, United States.
J Org Chem. 2013 Mar 15;78(6):2422-9. doi: 10.1021/jo3026059. Epub 2013 Feb 8.
The asymmetric total synthesis of the chlorinated [2.2.2]-diazabicyclic indole alkaloid (+)-malbrancheamide B is reported. Key to the synthesis is a domino reaction sequence that employs an aldol condensation, alkene isomerization, and intramolecular Diels-Alder cycloaddition. Diastereofacial selection between the azadiene stereofaces is enforced with a chiral aminal auxiliary. A formal 7-step (longest linear route) synthesis of (±)-malbrancheamide B is also reported.
报道了氯化[2.2.2]-二氮杂双环吲哚生物碱（+）-马布兰奇酰胺 B 的不对称全合成。该合成的关键是一个多米诺反应序列，其中包括醛缩合、烯烃异构化和分子内 Diels-Alder 环加成。氮杂二烯立体面之间的立体选择性通过手性亚胺辅助基来强制实现。还报道了（±）-马布兰奇酰胺 B 的正式 7 步（最长线性路线）合成。
