Palladium‐Catalyzed Aminocarbonylation of Aryl Chlorides at Atmospheric Pressure: The Dual Role of Sodium Phenoxide

Silver Cluster Catalysts for Green Organic Synthesis

“…Synthesis of amides is mostly based on activated acid derivatives (acid chlorides and anhydrides) or rearrangement reactions induced by an acid or base 72), 73) . Alternative procedures include the Staudinger ligation 74) , aminocarbonylation of aryl halides 75) , oxidative amidation of aldehydes 76) , and amidation of alcohols with excess amount of hydrogen acceptor 77) . However, all these methods require stoichiometric amounts of various reagents and lead to equimolar amounts of byproducts.…”

Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems

“…Amides are typically synthesized by coupling of activated carboxylic acid derivatives with amines. [2] Alternative strategies toward the synthesis of amides are the Staudinger reaction, [3] the Schmidt reaction, [4] Beckmann rearrangement, [5] aminocarbonylation of haloarenes, [6] alkenes [7] and alkynes, [8] oxidative amidation of aldehydes, [9] hydrative amide synthesis with alkynes [10] and the amidation of thio acids with azides. [11] However, most of these methods require an equimolar amount of various reagents and generate larger amounts of by-products as waste.…”

Selective Monoarylation of Primary Amines Using the Pd‐PEPPSI‐IPentCl Precatalyst

“…Therefore,w ed esigned as imple procedure in which 12 is first prepared prior to adding the other reagents and the reaction solvent. By using this protocol, 8 was isolated in 95 %yield and high selectivity (25:1 8/9 in crude reaction mixture;entry 9) after purification of the crude reaction mixture using silica gel column chromatography.A lthough phenoxide derivatives have been employed in carbonylation [16] and closely related etherification reactions, [17] we did not observe the etherification product of 12 with 6.P henoxides such as 12 possess similar pK b values as the inorganic carbonate and phosphate bases, but importantly they are much more soluble in organic solvents.D espite these merits,t here appear to be only al imited number of examples where they are used as basic additives in palladium-catalyzed amination reactions. [15a, 18] Using the productive results with Na-BHT,w ew ere able to develop arobust method for the amination of (hetero)aryl halides with primary aliphatic amines catalyzed by Pd-PEPPSI-IPent Cl complex 5.T he final conditions are shown at the top of Table 2.…”