Electrooxidative Ring-Opening and Strain-Release-Driven Skeletal Rearrangement of Cyclopropenes

We develop two distinct electrooxidative strategies for the ring-opening and strain-release-driven rearrangement of cyclopropenes when reacting with alcohols and trimethylsilyl azide, yielding gem-dialkoxyallylated compounds and tetrasubstituted alkenyl nitriles. The synthesis of allylated derivatives starts with the direct anodic oxidation of the cyclopropene ring to form a cyclopropene radical cation. This radical cation undergoes addition by an alkoxide (acting as a nucleophile) at the C2 position, followed by regioselective cleavage of the C1-C2 bond. For alkenyl nitriles, anodic oxidation of the radical precursor produces an azide radical that adds to the cyclopropene ring at the less-substituted C3 position. This leads to regioselective cleavage of the C1-C3 bond. Additionally, the postreaction modifications and the ability to synthesize deuterated allyl compounds further demonstrate the utility of these transformations.