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2.1.2.1.1.1.1 Palladium-Catalyzed Coupling Reactions

DOI: 10.1055/sos-SD-208-00078

Hay, M. B.; Hicks, J. D.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20132111.

Typical palladium catalysts for the N-arylation of primary aromatic amines with aryl iodides are generated from bidentate ligands [BINAP,[‌33‌] dppf,[‌34‌] Xantphos (5),[‌35‌] dppe,[‌36‌] or CyPF-tBu (4)[‌37‌]] or dialkyl(biaryl)phosphines[‌35‌] and a palladium precursor such as tris(dibenzylideneacetone)dipalladium(0) or palladium(II) acetate (Scheme 3). High catalytic activity has also been observed using precatalysts of type 1, even with catalyst loadings as low as 500 ppm.[‌38‌,‌39‌] These amination reactions typically employ strong bases such as sodium tert-butoxide, although weaker bases like cesium carbonate can be used when base-sensitive functional groups are present. The BrettPhos-based precatalyst 6 together with sodium tert-butoxide or cesium carbonate in toluene constitute fairly general conditions to facilitate the coupling of a variety of electronically diverse aryl iodides and anilines, including challenging couplings with electron-deficient aniline derivatives.

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References


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