Trans-chelating ligands in palladium-catalyzed carbonylative coupling and methoxycarbonylation of aryl halides

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

“…It has been demonstrated that the Pd complex PdCl 2 {P(OCMe 2 CMe 2 O)OC 6 H 4 NH 2 } with a H‐spirophosphorane ligand appears to be a highly efficient and selective precatalyst for the carbonylative Suzuki cross‐coupling reactions of aryl iodides with arylboronic acid and with sodium tetraphenylborate. The carbonylation reactions were performed under mild conditions compared to those of other Pd complexes with chelating P ligands . Diarylketones were obtained in high yields in 2 h under an atmospheric pressure of CO with a low amount of the catalyst.…”

“…However, the vast majority of known systems require a long reaction time, an unattractive amount of catalyst, and a relatively high pressure of CO . Among them, there is a large group of catalysts that contain P ligands mainly of the phosphine type . Catalytic systems that incorporate phosphine ligands along with a Pd precursor were also used .…”

“…Catalytic systems that incorporate phosphine ligands along with a Pd precursor were also used . In contrast, there are only a few examples of catalytic systems that contain phosphite‐based ligands …”

Methyl Salicylate as a Selective Methylation Agent for the Esterification of Carboxylic Acids

“…The methylation of 3-nitro-, 4-nitro-, 2-chloro-, 2-bromo-, 4-formyl-, and 4-(ethoxycarbonyl)benzoic acid proceeded smoothly to give the corresponding products 3i-n in 88-93% yields (entries 9-14). Alkylcarboxylic acids underwent the esterification as well as aromatic acids (entries [15][16][17][18][19][20]. The protocol was also applied to the esterification of methacrylic acid and cinnamic acid, giving the desired methyl methacrylate (3u) and methyl cinnamate (3v) in 72% and 79% yield respectively (entries 21 and 22).…”

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

“…Yellow oil. 1 (2,4-Dichlorophenyl)(phenyl)methanone (3i): [33] (4-Chlorophenyl)(phenyl)methanone (3n): [36] Yield: 81 % (35 mg). White solid, m.p.…”