Catalytic Oxidative Carbonylation of Amino Moieties to Ureas, Oxamides, 2‐Oxazolidinones, and Benzoxazolones

Abstract

The direct syntheses of ureas, oxamides, 2-oxazolidinones, and benzoxazolones by the oxidative carbonylation of amines, β-amino alcohols, and 2-aminophenols allows us to obtain high value added molecules, which have a large number of important applications in several fields, from very simple building blocks. We have found that it is possible to perform these transformations using the PdI2 /KI catalytic system in an ionic liquid, such as 1-butyl-3-methylimidazolium tetrafluoroborate, as the solvent, the solvent/catalyst system can be recycled several times with only a slight loss of activity, and the product can be recovered easily by crystallization.

Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

“…Ionic liquids (ILs) have been employed as reaction media in the oxidative carbonylation of amines to generate biphasic systems . In these reactions, the catalytic systems were constituted by a Pd 2+ catalyst, an IL, and in the case of Mancuso et al., an iodide salt as an additive . ILs constitute a special class of compounds that exhibit interesting physical and chemical properties for applications in areas such as catalysis, biomass processing, and electrochemistry .…”

“…Further support for the proposed mechanisms was provided by Didgikar et al . and Gabriele et al –. who both studied the oxidative carbonylation of amines with Pd 2+ /I − catalytic systems using O 2 as an oxidant and reported a correlation between the nucleophilicity and the reactivity of the substrate.…”

“…Ionic liquids (ILs) have been employed as reaction media in the oxidative carbonylation of amines to generate biphasic systems . In these reactions, the catalytic systems were constituted by a Pd 2+ catalyst, an IL, and in the case of Mancuso et al., an iodide salt as an additive .…”

One-Pot Synthesis of N,N′-dialkylureas via Carbonylation of Amines with CO2 Applying Y0.08Zr0.92O1.96 Mixed Oxide (YSZ-8) as a Heterogeneous Catalyst

“…In the past few years, a number of safer and more environmentally benign synthetic routes were invented [3], including carbonylation of amines with various carbonyl derivatives such as carbonyldiamide [4], acetoacetanilide [5], carbonate [6], urea [7], carbamate [8] etc. ; or with gaseous C 1 sources such as CO [9,10] or CO 2 [11]. Amongst them, direct carbonylation of amines by CO 2 is far more attractive from the standpoint of either environmental consideration or resource utilization [3].…”

(Z)-4-(Carbomethoxymethylene)-2-(4-fluorophenyl)-4H-benzo[d][1,3]oxazine

“…Over the years, we have successfully applied this effective methodology to access carbonylated compounds in a one-pot fashion [6][7][8][9][10][11][12][13]. In particular, some years ago, we reported a facile and efficient route for the synthesis of new functionalized benzo[d] [1,3]oxazines by in situ deprotection of 2-(trimethylsilanyl)ethynylaniline derivatives followed by palladium-catalyzed cyclizationalkoxycarbonylation [14].…”