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Synthesis of arylamines

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Recent Literature


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.


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.


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.