Categories: C-N Bond Formation >
Synthesis of amidines
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Recent Literature
2,2,2-Trifluoro- and trichloroethyl imidates, which are easily prepared by
reaction of a nitrile and a trihaloethanol in the presence of HCl, are excellent
reagents for the preparation of amidines under mild reaction conditions.
S. Caron, L. Wei, J. Douville, A. Ghosh, J. Org. Chem., 2010,
75, 945-947.
A method for the Pd-catalyzed N-arylation of both aryl and alkyl amidines with a
wide range of aryl bromides, chlorides, and triflates proceeds in short reaction
times and with excellent selectivity for monoarylation. A one-pot synthesis of
quinazoline derivatives via Pd-catalyzed N-arylation followed by addition of an
aldehyde to the crude reaction mixture is also demonstrated.
M. A. McGowan, C. Z. McAvoy, S. L. Buchwald, Org. Lett., 2012,
14, 3800-3803.
Microwave reactions of primary and secondary amines with
imidoylbenzotriazoles gave various polysubstituted amidines in good yields.
Convenient preparations of a variety of amides and imidoylbenzotriazoles
have also been developed using microwave irradiation under mild conditions
and short reaction times.
A. R. Katritzky, C. Cai, S. K. Singh, J. Org. Chem., 2006,
71, 3375-3380.
The reaction of hexamethyldisilazane with formamides and sulfonamides
provides sulfonylformamidines. This protocol can also be applied for
arylformamidine formation with anilines as substrates under optimized conditions.
The advantages of this method are high efficiency, good yields, and
applicability in large-scale operations.
Y.-C. Chou, W.-H. Lin, X.-Y. Lin, C.-L. Kuo, W.-Q. Zeng, I.-C. Lu, C.-F.
Liang, J. Org. Chem., 2022, 87,
15327-15332.
A silver-catalyzed, one-pot, four-component reaction of terminal alkynes,
TMSN3, sodium sulfinate, and sulfonyl azide provides amidines. A
possible cascade reaction mechanism consists of alkyne hydroazidation, sulfonyl
radical addition, 1,3-dipolar cycloaddition of TMSN3, and
retro-1,3-dipolar cycloaddition.
B. Liu, Y. Ning, M. Virelli, G. Zanoni, E. A. Anderson, X. Bi, J. Am. Chem. Soc.,
2019,
141, 1593-1598.
A mild, metal-free, multicomponent reaction provides N-acyl amidines
from nitroalkene derivatives, dibromo amides, and amines via formation of an
initial α,α-dibromonitroalkane intermediate that can undergo C-C bond cleavage.
This alternative approach toward N-acyl amidines enables rapid
construction of amidine frameworks with high diversity and complexity.
M. Zhou, J. Li, C. Tian, X. Sun, X. Zhu, Y. Cheng, G. An, G. Li, J. Org. Chem., 2019, 84,
1015-1024.
A catalyst-free hydroamination of N,N-disulfonyl ynamides with amines
gives N-sulfonylamidines. Alkyl amines react with N,N-disulfonyl
ynamides under mild conditions, whereas aryl amines require higher temperatures.
Y. Kong, L. Yu, J. Cao, Synthesis, 2014, 46,
183-188.
A silver-catalyzed or metal-free thermally promoted denitrogenation of N-sulfonyl-1,2,3-triazoles
enables a highly efficient synthesis of N-sulfonylamidines in the
presence of amines.
Y. Feng, W. Zhou, G. Sun, P. Liao, X. Bi, X. Li, Synthesis, 2017,
49, 1371-1379.
A N-trifluoromethylation of nitriles with PhICF3Cl
followed by DMAP-catalyzed capture with N-, O-, or S-centered nucleophiles enables an efficient
synthesis of a wide range of N-CF3 amidines, imidates, and
thioimidates.
R. Z. Zhang, W. Huang, R. X. Zhang, C. Xu, M. Wang, J. Sun, Org. Lett.,
2022, 24, 2393-2398.
Organic azides are easily and chemoselectively reduced to the corresponding
amines by reaction with dichloroindium hydride under very mild conditions.
γ-Azidonitriles give pyrrolidin-2-imines in an outstanding cyclization.
L. Benati, G. Bencivenni, R. Leardini, D. Nanni, M. Minozzi, P. Spagnolo, R.
Scialpi, G. Zanardi, Org. Lett.,
2006,
8, 2499-2502.
Related
Copper-catalyzed cross-coupling reactions of amidine salts with aryl iodides
give monoarylated amidines in good yields under ligand-free conditions. DMF was
the superior solvent for the N-arylation of benzamidines, while MeCN was
used in the formation of N-aryl amidines in good yield.
M. Cortes-Salva, C. Garvin, J. C. Antilla, J. Org. Chem., 2011,
76, 1456-1459.