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Direct Acyl Substitution of Carboxylic Acids: A Chemoselective O‐ to N‐Acyl Migration in the Traceless Staudinger Ligation
Author(s) -
Kosal Andrew D.,
Wilson Erin E.,
Ashfeld Brandon L.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201773
Subject(s) - chemistry , acylation , nucleophilic acyl substitution , azide , nucleophile , alkyl , staudinger reaction , carboxylic acid , electrophile , nucleophilic substitution , acyl chloride , sulfonyl , combinatorial chemistry , organic chemistry , chemoselectivity , catalysis , chloride
A chlorophosphite‐modified, Staudinger‐like acylation of azides involving a highly chemoselective, direct nucleophilic acyl substitution of carboxylic acids is described. The reaction provides the corresponding amides with analytical purity in 32–97 % yield after a simple aqueous workup without the need for a pre‐activation step. The use of chlorophosphites as dual carboxylic acid–azide activating agents enables the formation of acyl CN bonds in the presence of a wide range of nucleophilic and electrophilic functional groups, including amines, alcohols, amides, aldehydes, and ketones. The coupling of carboxylic acids and azides for the formation of alkyl amides, sulfonyl amides, lactams, and dipeptides is described.