COtab: Expedient and Safe Setup for Pd-Catalyzed Carbonylation Chemistry

Abstract

Bench-stable tablets (COtabs) have been developed for the rapid and safe production of carbon monoxide. The tablets can be made in less than 5 min without the use of a glovebox and only require a stock solution of an amine base to liberate a specific quantity of CO in a twochamber system. The COtabs were tested in five different carbonylation reactions and provided similar yields compared to literature procedures. Finally, a gram-scale reaction was conducted, as well as 13 C-isotope labeling of the anticancer drug, olaparib.

Visible-Light-Enabled Aminocarbonylation of Unactivated Alkyl Iodides with Stoichiometric Carbon Monoxide for Application on Late-Stage Carbon Isotope Labeling

“…As COgen is moisturesensitive and undergoes hydrolysis, a fresh batch of COgen was made before using. 15 To facilitate the visible-light chemistry in a parallel fashion, a photoreactor was constructed (Figure 1B,C). Blue lightemitting diodes (LEDs) surround a central compartment, which contains a heating block to enable the liberation of CO from COgen at 70 °C.…”

“…The generality of this method was further evaluated by performing the aminocarbonylation method with iodobenzene, and to our delight, morpholino(phenyl)methanone 13 was isolated with a good yield. Para-substituted aryl iodides, tertbutyl (4-iodobenzyl)carbamate and 1-iodo-4-methoxybenzene, were used to give good yields, 70% (14) and 69% (15), respectively.…”

“…The dual chamber system (COware (Figure A)) was used as previously described. As COgen is moisture-sensitive and undergoes hydrolysis, a fresh batch of COgen was made before using …”

Renewable Solvents for Palladium-Catalyzed Carbonylation Reactions

“…A range of renewable solvents were studied for carbonylative couplings of aryl bromides with arylboronic acids, amines (aminocarbonylation), and alcohols (alkoxycarbonylation) (Figure ). We decided to focus on Pd-based catalytic systems that have proven to be versatile catalysts for carbonylative couplings. ,− For safety reasons, the reactions were conducted in two chamber reactors (COware) developed in the group of Skrydstrup using stoichiometric quantities of CO generated ex situ from COgen (9-methyl-9 H -fluorene-9-carbonyl chloride) .…”

5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions

“…More recently, this group have developed a tablet form of 2 that contains tri-tert-butylphosphonium tetrauoroborate and Pd(OAc) 2 which allows convenient CO generation without the need for use of a glovebox for carbonylative transformations. 22 Herein, we report the development of readily accessible, stable norbornenone derivatives as efficient base-triggered CO donors as alternatives to 1 and 2 for palladium catalysed carbonylation reactions of aryl iodides using a twochamber reaction system without the need for glovebox equipment.…”