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.
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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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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.
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New aryl/heteroaryl C-N bond cross-coupling reactions via arylboronic acid/cupric acetate arylation
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