This reaction allows aryl carbon-heteroatom bond formation via an oxidative coupling of boronic acids, stannanes or siloxanes with N-H or O-H containing compounds in air. Substrates include phenols, amines, anilines, amides, imides, ureas, carbamates, and sulfonamides. The reaction is induced by a stoichiometric amount of copper(II) or a catalytic amount of copper catalyst which is reoxidized by atmospheric oxygen or another primary oxidant.
The Chan-Lam Coupling may be conducted at room temperature in air, which gives it a certain advantage over the Buchwald-Hartwig Cross Coupling.
Mechanism of the Chan-Lam Coupling
The reaction with a stoichiometric amount of copper(II) is also facilitated by oxygen, because reductive elimination from a copper(III) species is faster.
Spectroscopic Studies of the Chan-Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity
J. C. Vantourout, H. N. Miras, A. Isidro-Llobet, S. Sproules, A. J. B. Watson, J. Am. Chem. Soc., 2017, 139, 4769-4779.
Ligand- and Base-Free Copper(II)-Catalyzed C-N Bond Formation: Cross-Coupling Reactions of Organoboron Compounds with Aliphatic Amines and Anilines
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Copper(II) acetate catalyzes a coupling of arylboronic acids and amines in the presence of 2,6-lutidine as base, and myristic acid as an additive. Functionalized aniline substrates provided diarylamine coupling products in good yield, whereas alkylamines gave N-alkyl anilines in moderate yield.
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A Cu-catalyzed nondecarboxylative methylation of carboxylic acids with methylboronic acid proceeds in air as sole oxidant and offers a strategy for replacing toxic, electrophilic alkylating reagents. An isotope-labeling study supports an oxidative cross-coupling mechanism, in analogy to that proposed for Chan-Lam arylation.
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Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
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Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides
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An Efficient Base-Free N-Arylation of Imidazoles and Amines with Arylboronic Acids Using Copper-Exchanged Fluorapatite
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Microwave-assisted conditions enabled a simple, rapid, one-pot synthesis of arylaminomethyl acetylenes in very good yields using arylboronic acids, aqueous ammonia, propargyl halides, copper(I) oxide and water as the solvent within ten minutes.
Y. Jiang, S. Huang, Synlett, 2014, 25, 407-410.
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Copper-Catalyzed Nondecarboxylative Cross Coupling of Alkenyltrifluoroborate Salts with Carboxylic Acids or Carboxylates: Synthesis of Enol Esters
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Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations
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An Efficient Copper-Catalyzed One-Pot Synthesis of Diaryl Thioethers by Coupling of Arylboronic Acids with Potassium Ethyl Xanthogenate under Mild Conditions
L. Wang, W.-Y. Zhou, S.-C. Chen, M.-Y. He, Q. Chen, Synlett, 2011, 3041-3045.
A cross-coupling reaction of arylboronic acids with KSCN salt to yield aryl thiocyanates is catalyzed by copper acetate in the presence of 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. Various arylboronic acids were suitable under the reaction conditions.
N. Sun, H. Zhang, W. Mo, B. Hu, Z. Shen, X. Hu, Synlett, 2013, 24, 1443-1447.
Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines
T. Meng, L. A. Wells, T. Wang, J. Wang, S. Zhang, J. Wang, M. C. Kozlowski, T. Jia, J. Am. Chem. Soc., 2022, 144, 12476-12487.
Copper(I) Oxide Catalyzed N-Arylation of Azoles and Amines with Arylboronic Acid at Room Temperature under Base-Free Conditions
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New aryl/heteroaryl C-N bond cross-coupling reactions via arylboronic acid/cupric acetate arylation
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Comparison of Copper(II) Acetate Promoted N-Arylation of 5,5-Dimethyl Hydantoin and Other Imides with Triarylbismuthanes and Aryl Boronic Acids
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One-Pot Approach to 1,2-Disubstituted Indoles via Cu(II)-Catalyzed Coupling/Cyclization under Aerobic Conditions and Its Application for the Synthesis of Polycyclic Indoles
J. Gao, Y. Shao, J. Zhu, H. Mao, X. Wang, X. Lv, J. Org. Chem., 2014, 79, 9000-9008.
Copper-Catalyzed Reactions of Alkenyl Boronic Esters via Chan-Evans-Lam Coupling/Annulation Cascades: Substrate Selective Synthesis of Dihydroquinazolin-4-ones and Polysubstituted Quinolines
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