Arylation of carbonyls,o ne of the most common approaches towarda lcohols,h as received tremendous attention, as alcohols are important feedstocks and building blocks in organic synthesis.Despite great progress,there is still agreat gap to develop an ideal arylation method featuring mild conditions,g ood functional group tolerance,a nd readily available starting materials.W enow showthat electrochemical arylation can fill the gap.B yt aking advantage of synthetic electrochemistry,c ommercially available aldehydes (ketones) and benzylic alcohols can be readily arylated to provide ag eneral and scalable access to structurally diverse alcohols (97 examples, > 10 gram-scale). More importantly,convergent paired electrolysis,t he ideal but challenging electrochemical technology,was employed to transform low-value alcohols into more useful alcohols.D etailed mechanism study suggests that two plausible pathwaysa re involved in the redox neutral aarylation of benzylic alcohols.
An electrochemical oxidative dehydrogenative C(sp3)–H
amination reaction to construct trans-2,3-disubstituted
aziridines is reported, which avoids using external oxidants and generates
only hydrogen gas as the byproduct. With KI as the mediator and electrolyte,
the desired aziridines were prepared in good yields in an undivided
cell at room temperature. The potential value of this mild electrochemical
strategy was further highlighted by the gram-scale synthesis.
The hydrotrifluoromethylation of
benzyl-protected homoallylic alcohol
and amine derivatives catalyzed by 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) was developed. This reaction
delivered δ-fluoromethylated free alcohols and amines with in
situ deprotection of benzyl protecting group under mild irradiation
conditions. 4CzIPN was found to be a competent metal-free photoredox
catalyst for activating several types of fluoromethylation reagents
including CF3SO2Cl, Togni’s reagent,
and 2-bromo-2,2-difluoroacetate via oxidative quenching and also CF3SO2Na through reductive quenching to allow direct
hydrotrifluoromethylation of simple alkenes and Michael acceptors.
We reported an electrochemical intramolecular C-H amination approach to construct benzimidazole-fused phenanthridines. This electrochemical approach was compatible with variety of functional groups, including ester, silyl, thioether, pyridyl, amine groups. With...
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