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Silver-Catalyzed Decarboxylative Chlorination of Aliphatic Carboxylic Acids.
MedLine Citation:
PMID:  22316183     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
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 in order 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)2OTf, 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.
Authors:
Zhentao Wang; Lin Zhu; Feng Yin; Zhongquan Su; Zhaodong Li; Chaozhong Li
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-2-8
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  -     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-2-9     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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