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Silver-Catalyzed Decarboxylative Chlorination of Aliphatic Carboxylic Acids
Decarboxylative halogenation of carboxylic acids, the
Hunsdiecker
reaction, is one of the fundamental functional group transformations
in organic chemistry. As the initial method requires the preparations
of strictly anhydrous silver carboxylates, several modifications have
been developed to simplify the procedures. However, these methods
suffer from the use of highly toxic reagents, harsh reaction conditions,
or limited scope of application. In addition, none is catalytic for
aliphatic carboxylic acids. In this Article, we report the first catalytic
Hunsdiecker reaction of aliphatic carboxylic acids. Thus, with the
catalysis of AgÂ(Phen)<sub>2</sub>OTf, the reactions of carboxylic
acids with <i>t</i>-butyl hypochlorite afforded the corresponding
chlorodecarboxylation products in high yields under mild conditions.
This method is not only efficient and general, but also chemoselective.
Moreover, it exhibits remarkable functional group compatibility, making
it of more practical value in organic synthesis. The mechanism of
single electron transfer followed by chlorine atom transfer is proposed
for the catalytic chlorodecarboxylation