Remarkable ligand effect on the palladium-catalyzed double carbonylation of aryl iodides

Abstract

The use of t-Bu3P as a ligand dramatically improved the generality of the double carbonylation of aryl iodides, and Mo(CO)6 was also found to be effective as a CO source in the system.

SeO2 mediated efficient synthesis of amides and α-ketoamides of secondary amines with wide substrate scope

“…2-4 α-Ketoamides are synthesized from diverse substrates such as methyl-ketones, 5-10 aldehydes/arylglyox-als, [11][12][13][14][15][16] -ketoacids, [17][18][19][20] terminal alkynes, [21][22][23][24] cyanamides, 25 carbamoyl stannane/ silane with acid chlorides, [26][27][28] addition of aroyl to aryl-acetamides, 29 2,2-dibromo-1-aryl ethanones 30 and double carbonylation of aryl iodides. [31][32][33] Usually in these oxidative amidation, a co-oxidant is required. Recent advances in catalytic synthesis of α-ketoamides has been reviewed recently.…”

Pd‐Catalysed Mono‐ and Dicarbonylation of Aryl Iodides: Insights into the Mechanism and the Selectivity

“…In particular, the Pd‐catalysed dicarbonylation of aryl halides provides a direct method for the production of α‐ketoamides (Scheme , left),2, 3 which are precursors of biologically active compounds and several families of heterocycles 4. Most of the reported Pd catalysts are modified with phosphine ligands,5, 6, 7 which limit their application due to inherent problems with oxidation.…”

“…One of the most efficient phosphine‐based methods for dicarbonylation was discovered by Kondo and co‐workers,7 who used a Pd/P t Bu 3 catalyst in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as base. This reaction produced α‐ketoamides selectively without the need for high CO pressures.…”

Easy‐to‐Execute Carbonylative Arylation of Aryl Halides using Molybdenum Hexacarbonyl: Efficient Synthesis of Unsymmetrical Diaryl Ketones

“…Furthermore, it has also been employed in double carbonylation of aryl iodides in the presence of tBu 3 P as a ligand. [24] Although these carbonylation reactions in the presence of various nucleophiles were successful, to the best of our knowledge, direct synthesis of unsymmetrical diaryl ketones from carbonylative coupling of arylboronic acids and aryl halides using a solid carbon monoxide source have not been reported. As part of our continuing efforts in palladium-catalyzed C-C bond-forming reactions, [25] herein we set out to explore the methodology to construct diaryl ketone scaffolds through three-component cross-coupling of aryl and heteroaryl halides, Mo(CO) 6 as a solid carbon monoxide source, and boronic acids.…”