Science of Synthesis

Tomás-Gamasa, M., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 2, 27.

Buchwald has developed a series of monodentate dialkyl(biaryl)phosphine ligands that provide excellent results in a wide array of palladium-catalyzed N-arylation reactions (‌Scheme 15‌).[‌107‌,‌108‌] Of these ligands, two prove to be particularly useful in N-arylations of aliphatic amines. BrettPhos [2-(dicyclohexylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxybiphenyl] is an excellent ligand for palladium-catalyzed coupling reactions of aryl halides with primary aliphatic amines,[‌66‌,‌100‌] and RuPhos [2-(dicyclohexylphosphino)-2′,6′-diisopropoxybiphenyl] provides outstanding results in reactions of cyclic and acyclic secondary amine nucleophiles.[‌67‌,‌100‌] A high degree of functional group tolerance is observed in these reactions, although the appropriate base (LiHMDS, Cs2CO3, or K3PO4) must be employed in reactions of functionalized substrates (‌Scheme 16‌).[‌100‌]

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Me8	M	M8	Meee (e)	Meeee (%)	Mee
8-MM(MM8)8M8M8	Me	(MM8)8MM	88	88	[‌888‌]
8-MMM8M8	Me		88	88	[‌888‌]
8-MeMMM8M8	Me		8	88	[‌888‌]
8-M8MMMM8M8	Me		88	88	[‌888‌]
8-MeM8M8	M	8-MeM8MM8M8MM8	88	88e	[‌888‌]
8-MMM8M8	Me	(MM8)8MMe	8	88	[‌888‌]

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References