Abstract
Comprehensive SummarySkipped dienes are of great importance but remain challenging to synthesize because of the presence of a sp3 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.
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