Synthesis of Skipped Aminodienes by a Ni-Catalyzed Ring-Opening/Cross-Coupling Reaction of Vinylaziridines with Multifunctional Organoboronic Acids

Skipped dienes are of great importance but remain challenging to synthesize because of the presence of a sp(3) hybrid carbon between the two alkenes. Herein, we have developed the first nickel-catalyzed regio-, (E)-stereo- and linear-selective ring-opening/cross-coupling reaction of vinylaziridines with organoboronic acids under mild conditions to construct various skipped aminodienes. The reaction exhibits wide functional-group compatibility, and could be adapted for the introduction of skipped aminodiene functionality into bioactive molecules. In addition, the reaction could be carried out on a gram-scale, delivering the ring-opening products in high yields and with linear-selectivity (90% yield, l : b >20 : 1). Furthermore, DFT calculations and mechanistic experiments provided detailed insights into the mechanism.