Zhang Xueying, Zhang Zhansong, Song Jin-Na, Wang Zikun
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University Changchun 130024 China
School of Life Science, Jilin University Changchun 130012 China
Chem Sci. 2020 Jul 7;11(30):7921-7926. doi: 10.1039/d0sc02559c.
We report here a novel reductive radical-polar crossover reaction that is a reductive radical-initiated 1,2-C migration of 2-azido allyl alcohols enabled by an azidyl group. The reaction tolerates diverse migrating groups, such as alkyl, alkenyl, and aryl groups, allowing access to +1 ring expansion of small to large rings. The possibility of directly using propargyl alcohols in one-pot is also described. Mechanistic studies indicated that an azidyl group is a good leaving group and provides a driving force for the 1,2-C migration.
我们在此报告一种新型的还原自由基-极性交叉反应，该反应是由叠氮基引发的2-叠氮基烯丙醇的还原自由基引发的1,2-碳迁移反应。该反应能耐受多种迁移基团，如烷基、烯基和芳基，可实现从小环到大环的 +1 环扩展。文中还描述了一锅法直接使用炔丙醇的可能性。机理研究表明，叠氮基是一个良好的离去基团，并为1,2-碳迁移提供了驱动力。
