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N-arylation

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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.

An efficient copper(I) bromide catalyzed N-arylation of azoles with a variety of aromatic bromides and iodides under mild conditions displayed great functional group compatibility and excellent reactive selectivity.
H. Chen, D. Wang, X. Wang, W. Huang, Q. Cai, K. Ding, Synthesis, 2010, 1505-1511.

A copper-catalyzed N-arylation reaction of imidazole proceeds under very mild conditions in the absence of additional ligand. This protocol tolerates an array of thermally sensitive functional groups, but also achieves high chemoselectivity.
L. Zhu, G. Li, L. Luo, P. Guo, J. Lan, J. You, J. Org. Chem., 2009, 74, 2200-2202.

A mild, new aryl/heteroaryl C-N bond cross-coupling reaction via the arylboronic acid/cupric acetate arylation of N-H containing heteroarenes proceeds at room temperature exposed to air, and works for many heteroarenes and arylboronic acids providing good yields of N-arylated heteroarenes.
P. Y. S. Lam, C. G. Clark, S. Saubern, J. Adams, M. P. Winters, D. M. T. Chan, A. Combs, Tetrahedron Lett., 1998, 39, 2941-2944.

4,7-Dimethoxy-1,10-phenanthroline is an efficient ligand for the mild, copper-catalyzed N-arylation of imidazole with aryl iodides and bromides. Various hindered and functionalized imidazoles and aryl halides were transformed in good to excellent yields.
R. A. Altman, S. L. Buchwald, Org. Lett., 2006, 8, 2779-2782.

[Cu(OH)·TMEDA]₂Cl₂ catalyzes an intermolecular coupling of arylboronic acids with imidazoles in dichloromethane at room temperature to provide a variety of N-arylimidazoles in very good yields.
J. P. Collman, M. Zhong, Org. Lett., 2000, 2, 1233-1236.

N-Arylation of imidazoles and amines with arylboronic acids catalyzed by copper-exchanged fluorapatite (CuFAP) in methanol at room temperature gave N-arylimidazoles and N-arylamines in good yields. The use of various arylboronic acids demonstrated the versatility of the reaction.
M. L. Kantam, G. T. Venkanna, C. Sridhar, B. Sreedhar, B. M. Choudary, J. Org. Chem., 2006, 71, 9522-9524.

N-arylation of either aryl iodides or aryl bromides with common π-excessive nitrogen heterocycles (pyrroles, pyrazoles, indazoles, imidazoles, and triazoles) was successfully performed in good yield with catalysts derived from diamine ligands and CuI. General conditions were found that tolerate various functional groups and hindered substrates.
J. C. Antilla, J. M. Baskin, T. E. Barder, S. L. Buchwald, J. Org. Chem., 2004, 69, 5578-5587.

L-(-)-Quebrachitol (QCT) as a ligand enables a selective N-arylation of nitrogen-containing heterocycles with aryl halides in the presence of copper powder. Unactivated aryl chlorides can be converted using KOtBu instead of Cs₂CO₃ as base.
Q. Zhou, F. Du, Y. Chen, Y. Fu, W. Sun, Y. Wu, G. Chen, J. Org. Chem., 2019, 84, 8160-8167.

A palladium-catalyzed coupling of aryl triflates with pyrazole derivatives using tBuBrettPhos as a ligand provides N-arylpyrazoles in very good yields. The coupling products of 3-trimethylsilylpyrazole served as a useful template for syntheses of further N-arylpyrazole derivatives.
S. Onodera, T. Kochi, F. Kakiuchi, J. Org. Chem., 2019, 84, 6508-6515.

Copper-Promoted One-Pot Sandmeyer-Type Reaction for the Synthesis of N-Aryltriazoles
M. Cui, R. Wang, Q. Yang, C. Kuang, J. Org. Chem., 2022, 87, 9654-9662.

A catalyst-free and regioselective N arylation enables the synthesis of N²-aryl-1,2,3-triazoles in very good yields. This scalable postmodification protocol is effective for a wide range of substrates.
S. Roshandel, M. J. Lunn, G. Rasul, D. S. M. Ravinson, S. C. Suri, G. K. S. Prakash, Org. Lett., 2019, 21, 6255-6258.

Bu₄NI catalyzes regioselective N²-alkylations and N²-arylations of tetrazoles using tert-butyl hydroperoxide as a methyl source, alkyl diacyl peroxides as primary alkyl source, alkyl peresters as secondary and tertiary alkyl sources, and aryl diacyl peroxides as arylating source. These reactions proceed without pre-functionalization of the tetrazoles and in the absence of any metal catalysts.
S. Rajamanickam, C. Sah, B. A. Mir, S. Ghosh, G. Sethi, V. Yadav, S. Venkateramani, B. K. Patel, J. Org. Chem., 2020, 85, 2118-2141.

The use of diaryliodonium salts enables a simple, metal-free regioselective N²-arylation strategy for 5-substituted-1H-tetrazoles to provide 2-aryl-5-substituted-tetrazoles. Diaryliodonium salts with a wide range of both electron-rich and previously challenged electron-deficient aryl groups are applicable. A one-pot system achieves the synthesis of 2,5-diaryl-tetrazoles directly from nitriles.
R. A. Saikia, A. Dutta, B. Sarma, A. J. Takur, J. Org. Chem., 2022, 87, 9782-9796.

An extremely general, experimentally simple, and inexpensive catalyst system for the amidation of aryl halides and the N-arylation of a wide variety of heterocycles has been developed. This Cu-based catalyst system provides an excellent complement to the Pd-catalyzed methodology that has already been utilized in a number of applications.
A. Klapars, J. C. Antilla, X. Huang, S. L. Buchwald, J. Am. Chem. Soc., 2001, 123, 7727-7729.

L-methionine ligated Cu catalyzes C-N cross-couplings of aromatic as well as aliphatic amines including tautomerizable N-heteroarenes. The amino, carboxy, and sulfide functions were critical for the ligation efficiency.
G. N. Vaidya, A. Khan, H. Verma, S. Kumar, D. Kumar, J. Org. Chem., 2019, 84, 3004-3010.

Bulky, electron-rich phosphines as the supporting ligand in combination with Pd₂(dba)₃ enable N-arylation of indoles with aryl iodides, bromides, chlorides, and triflates.
D. W. Old, M. C. Harris, S. L. Buchwald, Org. Lett., 2000, 2, 1403-1406.

A decarboxylative N-arylation of indole-2-carboxylic acids with aryl halides proceeds efficiently in the presence of Cu₂O as the catalyst to give the corresponding N-aryl indoles in high yields. This method shows good functional group tolerance.
Y. Zhang, Z.-Y. Hu, X.-C. Li, X.-X. Guo, Synthesis, 2019, 51, 1803-1808.

The use of N,N′-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene (SIPr) as a ligand and tBuONa as the base for sequential palladium-catalyzed intra- followed by intermolecular aryl amination enables the synthesis of N-arylated five-, six- and seven-membered nitrogen heterocycles.
R. Omar-Amrani, R. Schneider, Y. Fort, Synthesis, 2004, 2257-2534.

Ultrasmall nanoclusters offer a high surface area and unsaturated active sites. A copper nanocluster-based catalyst enables C-N bond-forming reactions of aryl chlorides under visible-light irradiation at room temperature. A range of N-heterocyclic nucleophiles and electronically and sterically diverse aryl/hetero chlorides react to provide C-N coupling products in good yields.
A Sagadevan, A. Ghosh, P. Maity, O. F. Mohammed, O. M. Bakr, M. Rueping, J. Am. Chem. Soc., 2022, 144, 12052-12061.

A Rh/Pd/Cu catalyst system led to an efficient one-pot synthesis of dihydroquinolinones without any intermediate workup. The conjugate-addition/amidation/amidation reaction sequence is highly modular, divergent, and practical.
L. Zhang, L. Sonaglia, J. Stacey, M. Lautens, Org. Lett., 2013, 15, 2128-2131.

A mild Cu-catalyzed approach for the N-arylation of 2-pyridones with diaryliodonium salts proceeds readily at room temperature to provide N-arylpyridine-2-ones in very good yields.
S.-H. Jung, D.-B. Sung, C.-H. Park, W.-S. Kim, J. Org. Chem., 2016, 81, 7717-7724.

CuI-catalyzed coupling reactions of tetrabutylammonium pyridin-2-olates with aryl iodides allow an efficient synthesis of N-aryl pyridine-2-ones. This coupling reaction is mild, high-yielding, remarkably chemoselective (N- vs. O-arylation), and tolerates labile functional groups.
H. Zhang, B.-C. Chen, B. Wang, S. T. Chao, R. Zhao, N. Lim, B. Balasubramanian, Synthesis, 2008, 1523-1524.

Copper acetate promoted N-arylation of imides with boronic acids can be employed as a major method for the synthesis of N₃-aryl hydantoins.
H. M. Hügel, C. J. Rix, K. Fleck, Synlett, 2006, 2290-2292.