American Chemical Society
ol8b03159_si_002.pdf (4.58 MB)

Regioselective Metal-Free Aza-Heck Reactions of Terminal Alkenes Catalyzed by Phosphine Selenides

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journal contribution
posted on 2018-10-19, 00:00 authored by Tianyi Zheng, John R. Tabor, Zackary L. Stein, Forrest E. Michael
Phosphine selenides are introduced as an alternate class of selenium-based catalysts for the aza-Heck reaction of alkenes. Using these catalysts, a range of terminal alkenes react with NFBS to give oxidative amination products. Judicious choice of phosphine ligand gives greater regio- and stereoselectivity than with diphenyl diselenide, enabling the selective formation of E terminal enimides in high yields. Isotope-labeling experiments and measurements of kinetic isotope effects reveal that the reaction occurs stereospecifically via irreversible anti addition, followed by rate-determining syn elimination.