Categories: C-N Bond Formation > Amines >
Synthesis of arylamines
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CuI/4-hydroxy-l-proline-catalyzed coupling of aryl bromides and N-Boc
hydrazine takes place in DMSO to give N-aryl hydrazides. When aryl
iodides are employed, no ligand is required.
Under the catalysis of CuI/4-hydroxy-l-proline, the coupling reaction of aqueous
ammonia with aryl bromides proceeds smoothly to afford primary arylamines.
L. Jiang, X. Lu, H. Zhang, Y. Jiang, D. Ma, J. Org. Chem., 2009,
74, 4542-4546.
CuI-nanoparticles catalyze a selective synthesis of phenols, anilines, and
thiophenols from aryl halides in the absence of both ligands and organic
solvents. Anilines were formed selectively with ammonia competing with
hydroxylation and thiophenols were generated selectively with sulfur powder
after subsequent reduction competing with hydroxylation and amination.
H.-J. Xu, Y.-F. Liang, Z.-Y. Cai, H.-X. Qi, C.-Y. Yang, Y.-S. Feng, J. Org. Chem., 2011,
76, 2296-2300.
A complex generated from Pd[P(o-tol)3]2 and the
alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for
the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates.
The couplings with this catalyst conducted with a solution of ammonia in dioxane
form primary arylamines from various aryl electrophiles in high yields.
G. D. Vo, J. F. Hartwig, J. Am. Chem. Soc., 2009,
131, 11049-11061.
A facile and practical copper powder-catalyzed Ullmann amination of aryl halides
with aqueous methylamine and other aliphatic primary amines under organic
solvent- and ligand-free condition at 100°C and in air gave N-arylamines
as sole products in very good yields. The presence of a small amount of air is
essential. Secondary amines and aniline are not reactive. Sensitive substituents
are tolerated.
J. Jiao, X.-R. Zhang, N.-H. Chang, J. Wang, J.-F. Wei, X.-Y. Shi, Z.-G. Chen, J. Org. Chem., 2011,
76, 1180-1183.
CuI/DMPAO-Catalyzed N-Arylation of Acyclic Secondary Amines
Y. Zhang, X. Yang, Q. Yao, D. Ma, Org. Lett., 2012,
14, 3056-3059.
In the presence of Pd(OAc)2, PhB(OH)2, and a hindered and
electron-rich MOP-type ligand, a variety of primary aryl amines reacted with
various aryl tosylates to form the corresponding secondary aryl amines in high
yields with high selectivity. Furthermore, the catalyst system was also
efficient for the arylation of indoles and hydrazones with aryl tosylates.
X. Xie, G. Ni, F. Ma, L. Ding, S. Xu, Z. Zhang, Synlett, 2011,
955-958.
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.
A rhodium-catalyzed amination reaction of aryl halides with amines takes place
in the presence of a N-heterocyclic carbene ligand. The active metal
species responsible for the reaction progress was identified. This convenient
and mild procedure for Rh-catalyzed N-arylation displays a wide range of
substrate scope and high degree of functional group tolerance.
M. Kim, S. Chang, Org. Lett., 2010,
12, 1640-1643.
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.
A nickel complex derived from dppf, along with NaOt-Bu as the base,
enabled challenging aminations of aryl sulfamates. Palladium-catalyzed
aminations of imidazolylsulfonates with rac-BINAP as the ligand offer an
improved functional group tolerance.
L. Ackermann, R. Sandmann, W. Song, Org. Lett., 2011,
13, 1784-1786.
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.
A facile metal-free oxidative amination of benzoxazole by activation of C-H
bonds with secondary or primary amines in the presence of catalytic iodine in
aqueous tert-butyl hydroperoxide proceeds smoothly at ambient temperature
under neat reaction condition to furnish products in high yields. This
user-friendly method produces only tertiary butanol and water as byproducts.
M. Lamani, K. R. Prabhu, J. Org. Chem., 2011,
76, 7938-7944.
