Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
J Am Chem Soc. 2012 Sep 19;134(37):15572-80. doi: 10.1021/ja306881u. Epub 2012 Sep 6.
A general and high yielding annulation strategy for the synthesis of various carbo- and heterocycles, based on an intramolecular aryne ene reaction is described. It was found that the geometry of the olefin is crucial to the success of the reaction, with exclusive migration of the trans-allylic-H taking place. Furthermore, the electronic nature of the aryne was found to be important to the success of the reaction. Deuterium labeling studies and DFT calculations provided insight into the reaction mechanism. The data suggests a concerted asynchronous transition state, resembling a nucleophilic attack on the aryne. This strategy was successfully applied to the formal synthesis of the ethanophenanthridine alkaloid (±)-crinine.
描述了一种基于分子内环芳炔-烯烃反应的通用且高产的环化策略，用于合成各种碳环和杂环化合物。研究发现，烯烃的几何形状对反应的成功至关重要，反式烯丙基-H 发生了特异性迁移。此外，芳炔的电子性质对反应的成功也很重要。氘标记研究和 DFT 计算为反应机制提供了深入的了解。数据表明，协同非同步过渡态类似于芳炔的亲核进攻。该策略成功地应用于乙醇菲啶生物碱（±）-可丽宁的形式合成。
