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

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 N-2 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.

Automated summary

This study reported a metal-free synthesis method for producing methylenecyclobutane containing tetrasubstituted alkenyl nitriles using a strain-release driven addition reaction of [1.1.1]propellane. The protocol could be scaled up to gram quantities and the resulting alkenyl nitriles were capable of undergoing various derivatization reactions, offering a wide range of possible transformation reactions.