Trifluoromethanesulfinyl chloride (CF3SOCl) has been introduced as a new reagent for C−H trifluoromethylthiolation of indoles, thiophenes, and ketones under catalyst‐free conditions and in the absence of reductant. The disproportionation of CF3SOCl to CF3SO2Cl and CF3SCl provides two pathways for the trifluoromethylthiolation. Direct trifluoromethylthiolation with CF3SCl or trifluoromethylsulfoxidation with CF3SOCl is followed by reduction with CF3SOCl. This reagent can be used to functionalize benzothiophenes, benzofurans, and indenes under the promotion of Ag2CO3. It can also be used for trifluoromethylthiolation of thiols and benzeneselenols, and 1,2‐bifunctional chlorotrifluoromethylthiolation of indoles, styrenes, and alkyenes. The method can also be extended for difluorometylthiolation reactions using CF2HSOCl.
Metal-free trifluoroethylthiolation with fluorinated sulfinate salt NaSOCHCF under reductive conditions has been developed. The strategy enables the installation of the SCHCF moiety efficiently to form a number of unexplored stable trifluoroethylthiolated heterocycles, arenes, and thiols, which have the potential to be a new series of fluorine-containing chemical entities for medicinal chemists.
An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbonheteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B 2 pin 2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance.
The
fluoromethoxymethylation of nitrogen heterocyclic compounds
with fluoromethyl iodide has been reported for the first time. In
this reaction, a number of unexplored fluoromethoxymethylated nitrogen
heterocyclic compounds including indoles, carbazoles, and 1H-indazoles were efficiently formed. Mechanistic studies
indicated that this transformation consists of electrophilic monofluoromethylation,
rapid hydrolysis, and another electrophilic monofluoromethylation.
This method makes it possible to synthesize complex bioactive molecules
containing a CH2OCH2F group, which have the
potential to be a new series of fluorine-containing chemical entities
for medicinal chemists.
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