Electrochemical Oxidation Enables Regioselective 1,3-Hydroxyfunctionalization of Cyclopropanes

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

“…Instead of attempting to trap the C-centered radical, further oxidation would generate the corresponding carbocation, which upon reaction with a nucleophilic alkyne would form the product (Scheme 1B, reaction 3). Based on precedence in the literature, this method should allow to transfer efficiently both aryl-and alkyl-substituted alkynes [41][42][43][44]. On the other hand, the nature of the alkene might be limited as it would strongly influence the oxidation potential of the carbon radical and the stability of the resulting carbocation.…”

Electrochemical Formation of Oxazolines by 1,3-Oxyfluorination of Non-activated Cyclopropanes

“…Oxyamination of arylcyclopropanes was established by Zhou et al, using electrochemical oxidation conditions . The same approach was used for oxyhalogenation and oxyalkynylation reactions of arylcyclopropanes by Sheng et al as well as the green synthesis method of β-hydroxy ketones by Huang et al and 1,3-diols by Cai et al A few examples for electrochemical oxidation of cyclopropane integrated into polycyclic systems are known; however, these are limited to the strained compounds with an increased highest occupied molecular orbital (HOMO) level. , Because the high oxidation potential of non-activated cyclopropanes prevents their selective electrochemical activation in the presence of other functional groups, we envisioned electrochemical generation of a reactive species, which would be engaged in the reaction with a C–C bond. For this purpose, we explored cyclopropane substrate 3 bearing benzamide functionality, which could be oxidized to an amidyl radical (Figure ).…”