Abstract: | A unique combination of steric and electronic properties appears to determine the effectiveness of phosphanyl-substituted biphenyls as ligands in palladium-catalyzed aminations and Suzuki coupling of aryl chlorides at room temperature Eq. (1)]. The oxidative addition step is greatly accelerated, and transmetalation (or Pd−N bond formation) and reductive elimination processes are facilitated. Use of these ligands allows for Suzuki coupling at very low catalyst loadings (as little as 10−6 mol % Pd). R″=cyclohexyl, tert-butyl. |