The C−O bond cleavage for activation of alcohols is synthetically useful and practically challenging. This work describes carbazate as a new type of electrochemically activated alkylating agent derived from ubiquitous alcohols for direct functionalization of heteroarenes under mild electrolytic conditions. The simple undivided cell at low oxidative potentials with carbon/platinum electrode set‐ups offers excellent substrate tolerance, affording a variety of primary, secondary and tertiary alkyl‐decorated heterocycles in good chemical yields. Furthermore, the mechanism for this electrochemical deoxyalkylation reaction has been investigated.
An efficient electrochemical 1,2-sulfonylation/alkynylation of alkenes via radical 1,4-alkynyl migration of alkynyl-substituted tertiary alcohols is described, which used sodium sulfinates as sulfonyl sources affording the corresponding α-sulfonyl-β-alkynylated products in moderate to excellent yields. This electrochemical reaction proceeds smoothly without the use of any metal catalyst, additive and oxidant and thus represents a new and eco-friendly strategy for the difunctionalization of unactive olefins, and also the first example of the electrochemical distal radical migration reaction.
A regioselective synthesis of 3-fluorinated imidazo[1,2-a]pyridines using 1-chloromethyl-4-fluoro-1,4-diazoniabi cyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) as the fluorinating reagent in aqueous condition is described. In the presence of DMAP, the reaction mainly gave monofluorinated product via electrophilic fluorinated process in moderate to good yields.
An electrochemical homo-coupling reaction of imidazopyridine heterocycles has been developed for the synthesis of biheteroaryls. This reaction features good compatibility, high yields and excellent regioselectivities, which provides an efficient access to biheteroaryl compounds.
A regioselective alkoxycarbonylation of imidazoheterocycles using carbazates as ester group sources in DMSO was developed, in which an inexpensive FeCl2·4H2O was used as the catalyst and (NH4)2S2O8 was the oxidant. The reaction proceeded smoothly under an air atmosphere to give the 3-alkoxycarbonylated products in moderate to good yields.
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