瞬态C3铵烯醇盐的[1,5]σ迁移碳重排

Wicker Garrit, Zhou Rundong, Schoch Roland, Paradies Jan

Department of Chemistry, Paderborn University, Warburger Strasse 100, 33098, Paderborn, Germany.

Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202204378. doi: 10.1002/anie.202204378. Epub 2022 Jun 10.

The stereospecific sigmatropic [1,5] carbon shift of C3 ammonium enolates is discovered. According to mechanistic, kinetic and computational experiments, this new rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza-Michael addition. This intermediate rapidly undergoes [1,5] sigmatropic carbon migration to furnish the respective tetrahydroquinoline-4-ones with excellent diastereoselectivities of d.r. >99 : 1 and in 61-98 % yield.

发现了C3铵烯醇盐的立体专一性[1,5]碳迁移。根据机理、动力学和计算实验，这种新的重排反应是通过分子内氮杂-Michael加成催化生成瞬态C3铵烯醇盐进行的。该中间体迅速经历[1,5]碳迁移，以优异的非对映选择性（d.r.>99:1）和61-98%的产率得到相应的四氢喹啉-4-酮。