Alkoxycarbonylation Of Aryl Iodides Research Articles

Gas‐Free Amino‐ and Alkoxycarbonylation of Aryl Iodides in a Bioinspired Deep Eutectic Solvent with Mo(CO)6 as a Safe CO Source

AbstractThe Pd‐catalyzed amino‐ and alkoxycarbonylation of aryl iodides has been exploited, for the first time, in a bioinspired Deep Eutectic Solvent and under gas‐free conditions, by using Mo(CO)6 as the CO source. The method allows for the preparation of carboxylic amides and esters in high yields (up to 99 %), short reaction time (2 h) and under mild reaction conditions (80 °C), with a low catalyst loading (2.5 mol %). Noteworthy, in the case of N‐hexylbenzamide, it has been demonstrated that both the catalyst and DES can be used for four consecutive runs, with a moderate decrease of catalytic efficiency. The methodology has been also applied to the preparation of an Active Pharmaceutical Ingredient used for the treatment of human scabies and lice.

Integrative Photoreduction of CO2 with Subsequent Carbonylation: Photocatalysis for Reductive Functionalization of CO2.

Efficient conversion of CO2 into fuels and chemicals with solar energy would be promising, but also faces great challenge. In this context, we describe the photoreductive functionalization of CO2 to construct new C-C, C-N, and C-O bonds through the respective Pd-catalyzed Suzuki carbonylation, aminocarbonylation, and alkoxycarbonylation of aryl iodides with CO in situ generated through the photoreduction of CO2 . This protocol opens up an alternative avenue for CO2 utilization by harnessing solar energy.

Reagent-Enabled ortho-Alkoxycarbonylation of Aryl Iodides via Palladium/Norbornene Catalysis

Summary Aryl carboxylic acid derivatives are common organic building blocks and important structural motifs found in various biologically important molecules. Herein, we report a distinct method for preparing aryl carboxylic acid derivatives through ortho -alkoxycarbonylation of aryl iodides via palladium/norbornene catalysis, which is enabled by a carefully tuned mixed-anhydride reagent. Using a sterically hindered acyl leaving group realizes selective C–O cleavage, allowing the carboxyl (instead of the acyl) group to be transferred. This method exhibits a board substrate scope and high functional-group compatibility. In addition, this approach provides direct access to macrolactones. Preliminary success with the corresponding aminocarbonylation is also achieved.

Hydroxy- and alkoxycarbonylation of aryl iodides catalyzed by polymer-supported palladium

The efficient carbonylation of aryl iodides catalyzed by palladium immobilized on polymers in water or methanol under very mild conditions is reported. The catalyst can be recycled several times without loss of activity.

A simple and efficient recyclable phosphine-free catalytic system for alkoxycarbonylation and carbonylative Sonogashira coupling reactions of aryl iodides

Using palladium on charcoal (Pd/C) and triethylamine as a novel, efficient, versatile, recyclable, and phosphine-free catalytic system, we carried out the alkoxycarbonylation of aryl iodides (alcohols or phenols as nucleophiles) and the carbonylative Sonogashira coupling reaction of aryl iodides with terminal alkynes, affording the corresponding aryl esters and α , β -alkynyl ketones in good to excellent yields under mild conditions. We found that both electron-withdrawing and electron-donating substituents on phenol enhanced the phenoxycarbonylation of iodobenzene. The recyclability of Pd/C was also demonstrated.