Molybdenum-Mediated Carbonylation of Aryl Halides with Nucleophiles Using Microwave Irradiation

Abstract

A new, efficient, and practical molybdenum-mediated carbonylation of aryl and heteroaryl halides with a variety of nucleophiles is described using microwave irradiation. A range of reactions illustrating the wide scope of this chemistry were carried out and proceeded in good to excellent yields.

Microwave irradiation as a sustainable tool for catalytic carbonylation reactions

“…Aminocarbonylation of aryl triflate with several nucleophiles.Roberts[55] reported a molybdenum-mediated carbonylation of aryl halides with a variety of nucleophiles, in the absence of palladium catalysts, using only microwave irradiation. The reactions were carried out with a 1:1:2 ratio of Mo(CO)6, aryl halide (iodide and bromide) and benzylamine, using 1,4-dioxane as solvent, and the corresponding benzylamides of type 56 were obtained in good yields.…”

“…To achieve full conversions aryl iodides required a temperature of 160 °C and 3h, whereas aryl bromide required a temperature of 200 °C and 5 h, both with 50 W of MW power. It should be noted that the use of Mo(CO) 5 Cl·NEt 4 instead of Mo(CO) 6 alowed a significant improvement on the reaction yields (Scheme 28)[55].Scheme 28. Mo(CO) 6 -mediated aminocarbonylation reaction of aryl halides using benzylamine as nucleophile.…”

Synthesis and reactivity of (pyrazol-1-yl)acyl iron complexes

“…2, which shows the pyridyl nitrogen atom occupies the position trans to the acyl group with the angle C(3)ÀFe(1)ÀN(1) of 160.51 (9) . The shortest distance between H 6 of pyridyl and 3-methyl protons of pyrazolyl is 2.771 Å, suggesting the NOE correlation between these protons as shown by the NOE experiments.…”

“…Found: C, 62.94; H, 4.51; N, 7.23%.3.11. Synthesis of CH 2 (CO) (3,5-Pr i 2 Pz)Fe(CO) (PPh 3 ) (SPy)(9) …”

Highly Efficient Microwave-Assisted CO Aminocarbonylation with a Recyclable Pd(II)/TPP-β-Cyclodextrin Cross-Linked Catalyst

“…Another class of solid in situ CO-releasing reagents are metal carbonyls, [33][34][35][36][37][38][39] which are currently the best alternative to CO-gas for aminocarbonylation. [40][41] These inorganic metal carbonyls and their derivatives are nevertheless CO releasers and relatively expensive.…”