通过中间体1,4-恶嗪酮的环加成/环反转反应合成愈创吡啶生物碱鲁佩斯汀M和L。
Synthesis of Guaipyridine Alkaloids Rupestine M and L by Cycloaddition/Cycloreversion of an Intermediate 1,4-Oxazinone.
作者信息
Scheerer Jonathan R, Leeth Ella B, Sprow Jennifer A
机构信息
Department of Chemistry, William & Mary, P.O. Box 8795, Williamsburg, VA 23187, USA.
出版信息
Synthesis (Stuttg). 2023 Aug;55(15):2319-2324. doi: 10.1055/s-0042-1751413. Epub 2023 Feb 2.
Abstract
A new method to prepare 1,4-oxazinone intermediates was developed based on aza-conjugate addition of β-amino alcohols to electron-deficient alkyne precursors. A tandem intramolecular cycloaddition/cycloreversion reaction sequence was evaluated, leading to the synthesis of the guaipyridine alkaloid natural products rupestine M and L. Starting from (-)-citronellal and thus a known configuration of the C5 stereocenter, a revised absolute configuration of natural rupestine L is suggested based on optical rotation.
摘要
基于β-氨基醇对缺电子炔烃前体的氮杂共轭加成，开发了一种制备1,4-恶嗪酮中间体的新方法。评估了串联分子内环加成/环反转反应序列，从而合成了愈创吡啶生物碱天然产物鲁佩斯汀M和L。从（-）-香茅醛出发，因此C5立体中心具有已知构型，基于旋光性提出了天然鲁佩斯汀L的修正绝对构型。
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