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 Ag(Phen)(2)OTf, the reactions of carboxylic acids with t-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.
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People’s Republic of China.
Zhentao
Z
Wang
Lin
L
Zhu
Feng
F
Yin
Zhongquan
Z
Su
Zhaodong
Z
Li
Chaozhong
C
Li
D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D003653:Decarboxylation; D054879:Halogenation; D006843:Hydrocarbons, Chlorinated / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism
D002264:Carboxylic Acids; D006843:Hydrocarbons, Chlorinated; D009942:Organometallic Compounds; D012834:Silver