Yuanyuan Hu, Bingwei Zhou, Hui Chen,* and Congyang Wang*

Since 1987, stoichiometric cyclomanganation of ketones and following reactions with olefins in the presence of palladium salts or trimethylamine N-oxide (Me₃N⁺O^–) had been reported, while the catalytic versions remain untouched so far. Herein, the first manganese-catalyzed redox-neutral C-H olefination of ketones with unactivated alkenes is described, which shows a distinct reactivity with its parent stoichimetric reactions. Remarkably, mechanistic experiments and DFT calculations uncovers a unique Concerted Bis-Metalation Deprotonation (CBMD) mechanism of Mn-Zn-enabled C-H bond activation.

This work has been published in Angew. Chem. Int. Ed. 2018, 57, 12071.