Synthesis of tetrasubstituted alkenyl nitriles via cyanocarbene addition of [1.1.1]propellane

Abstract

Herein, we report the metal-free synthesis of methylenecyclobutane containing tetrasubstituted alkenyl nitriles via a strain-release driven addition reaction of [1.1.1]propellane under mild conditions. Using this strategy, TMSN₃ was shown to interact with various hypervalent iodine(III) alkyne species to generate cyanocarbene upon N₂ evolution. The resulting cyanocarbene intermediate was then trapped by [1.1.1]propellane to produce tetrasubstituted alkenyl nitriles. This protocol could be scaled up to gram quantities and the resulting alkenyl nitriles were shown to be able to undergo various derivatization reactions, offering a plethora of possible transformation reactions.