ORGANIC
LETTERS
2012
Vol. 14, No. 12
3202–3205
Boric Acid: A Highly Efficient Catalyst
for Transamidation of Carboxamides
with Amines
Thanh Binh Nguyen,* Jonathan Sorres, Minh Quan Tran, Ludmila Ermolenko, and
Ali Al-Mourabit
Centre de Recherche de Gif-sur-Yvette, Institut de Chimie des Substances Naturelles,
CNRS, 91198 Gif-sur-Yvette Cedex, France
Received May 11, 2012
ABSTRACT
A novel method of transamidation of carboxamides with amines using catalytic amounts of readily available boric acid under solvent-free
conditions has been developed. The scope of the methodology has been demonstrated with (i) primary, secondary, and tertiary amides and
phthalimide and (ii) aliphatic, aromatic, cyclic, acyclic, primary, and secondary amines.
Amide linkage is one of the most important functional
groups in chemistry and plays a central role in living
systems.1 It is usually created by reactions of amines with
carboxylic acid derivatives (chlorides, anhydrides or esters
or acids),2,3 alcohols,4 or aldehydes.5
Transamidation is an attractive tool in synthetic organic
chemistry. However, the high inertness of the amide func-
tion hampered such transformations under thermal non-
catalytic conditions.6 Great efforts have been made to
develop more convenient procedures that allow the reac-
tions to take place at relatively lower temperatures by
utilizing activating reagents or catalysts.7 Despite their
wide scope, these protocols involved either energeti-
cally favorable systems (ring-opening of four-membered
rings,7d,e intramolecular assitance,7f or both factors) or
the use of moisture-sensitive and/or expensive activation
reagents (2ꢀ3 equiv; borate esters,7a dialkylformamide
dialkyl acetals,7b AlCl3,7g AlMe37c). The reaction can also
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r
10.1021/ol301308c
Published on Web 06/07/2012
2012 American Chemical Society