Categories: C-N Bond Formation > Amines >
Synthesis of arylamines
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The arylation of N-H and O-H containing compounds at room temperature with
phenylboronic acids is promoted in the presence of cupric acetate and a tertiary
amine. Substrates include phenols, amines, anilines, amides, imides, ureas,
carbamates, and sulfonamides.
D. M. T. Chan, K. L. Monaco, R.-P. Wang, M. P. Winteres, Tetrahedron Lett.,
1998, 39, 2933-2936.
An efficient, transition metal catalyst-free amination of aryl halides under
microwave irradiation is a particularly powerful method for the coupling of
electron-rich aryl halides with various amines. Meta-substituted anilines
have been prepared from ortho- or para-substituted phenylhalides.
A mechanism via a benzyne intermediate has been proposed.
L. Shi, M. Wang, C.-A. Fan, F.-M. Zhang, Y.-Q. Tu, Org. Lett., 2003,
5, 3515-3517.
A catalyst system based on a new biarylmonophosphine ligand shows excellent
reactivity for C-N cross-coupling reactions. This catalyst system enables the
use of aryl mesylates as a coupling partner and permits a highly selective
monoarylation of an array of primary aliphatic amines and anilines at low
catalyst loadings and with fast reaction times.
B. P. Fors, D. A. Watson, M. R. Biscoe, S. L. Buchwald, J. Am. Chem. Soc., 2008,
130, 13552-13554.
A silane-promoted nickel-catalyzed amination of aryl chlorides with a catalytic
amount of Ni(acac)2 and 3,5,6,8-tetrabromo-1,10-phenanthroline as
ligand in the presence of polymethylhydrosiloxane gives the desired (het)arylamines
in good yields. The reaction is sensitive to the nature and amount of the silane
promoter.
G. Manolikakes, A. Gavryushin, P. Knochel, J. Org. Chem., 2008,
73, 1429-1434.
Air- and moisture-stable Ni(II)-(σ-aryl) complexes, associated with N-heterocyclic
carbene ligands, produce a catalytically active Ni(0) species in situ for an
efficient amination of aryl chlorides with anilines and secondary cyclic amines
under mild conditions.
C. Chen, L-M. Yang, J. Org. Chem., 2007,
72, 6324-6327.
Aryl triflates substituted with both electron-poor and electron-rich groups are
effectively converted to the corresponding anilines under microwave irradiation
in 1-methyl-2-pyridone (NMP) without base and catalyst. It is noteworthy that
halogenated aryl triflates chemoselectively afford halogenated anilines.
G. Xu, Y.-G. Wang, Org. Lett., 2004, 6, 985-987.
N-Arylation of azoles and amines with arylboronic acids was efficiently
carried out with heterogeneous copper(I) oxide in methanol at room temperature
under base-free conditions. Various arylboronic acids and amines were converted
to the corresponding N-arylazoles and N-arylamines in very good
yields, demonstrating the versatility of the reaction.
B. Sreedhar, G. T. Venkanna, K. B. S. Kumar, V. Balasubrahmanyam, Synthesis, 2008,
795-799.
The reaction of di-tert-butyl dicarbonate or a chloroformate and
sodium azide with an aromatic carboxylic acid produces the corresponding
acyl azide. The acyl azide undergoes a Curtius rearrangement to form an
isocyanate derivative which is trapped either by an alkoxide or by an amine
to form the aromatic carbamate or urea.
H. Lebel, O. Leogane, Org. Lett., 2006,
8, 5717-5720.
An efficient, mild and transition-metal-free N-arylation of amines,
sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has
been achieved by using various o-silylaryl triflates in the presence of CsF.
Z. Liu, R. C. Larock, J. Org. Chem., 2006,
71, 3198-3209.
A copper-catalyzed electrophilic amination of simple and functionalized aryl,
heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl
diorganozinc nucleophiles with R2NOC(O)Ph and RHNOC(O)Ph reagents
as electrophilic nitrogen sources provides tertiary and secondary amines,
respectively, in generally good yields. In many cases, the product may be
isolated analytically pure after a simple extractive workup. A Cu-catalyzed
amination of Grignard reagents using cocatalysis by ZnCl2 is
described.
A. M. Berman, J. S. Johnson, J. Org. Chem.,
2006,
71, 219-224.
Zn[N(SiMe3)2]2 is a mild ammonia equivalent and base for the
palladium-catalyzed amination of aryl halides and triflates. The combination of Zn[N(SiMe3)2]2 and LiCl coupled with aryl
halides containing base-sensitive functionality in high yields.
D.-Y. Lee, J. F. Hartwig, Org. Lett., 2005,
7, 1169-1172.
The NiCl2(PPh3)2-PPh3-catalyzed cross-coupling of bromomagnesium diarylamides, generated in situ from
diarylamines, with aryl bromides or iodides is an inexpensive, convenient, and practical method
for the synthesis of triarylamines.
C. Chen, L.-M. Yang, Org. Lett., 2005,
7, 2209-2211.
1,1,1-Trimethylhydrazinium Iodide: A Novel, Highly Reactive Reagent for
Aromatic Amination via Vicarious Nucleophilic Substitution of Hydrogen
P. F. Pagoria, A. R. Mitchell, R. D. Schmidt, J. Org. Chem., 1996,
61, 2934-2935.
Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion
using Ts2O-tBuNH2 followed by in situ deprotection
with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity,
and with good functional group compatibility.
J. Yin, B. Xiang, M. H. Huffman, C. E. Raab, I. W. Davies, J. Org. Chem., 2007,
72, 4554-4557.
