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• 201230-82-2 carbon monoxide 
• 6310-21-0 2-(1,1-dimethylethyl)-benzenamine 
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Relevant academic research and scientific papers

Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)?H Activation

The 1,4-palladium shift strategy allows the functionalization of remote C?H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp3)?H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product.

Palladium-catalyzed oxidative carbonylation of alkyl and aryl indium reagents with CO under mild conditions

CO now can react with organoindium reagents. A novel palladium-catalyzed oxidative carbonylation reaction of organoindium reagents by CO gas with desyl chloride as oxidant was developed in supplementation with the classical methods for preparation of carboxylic acid derivatives. Primary, secondary alkyl indium reagents with β-hydrogens and aryl indium reagents were suitable substrates, and the reaction could be carried out at 60°C under 50 psi CO. Carbonylation of alkyl indium reagents can occur smoothly without additional base. Although the indium reagents were prepared from corresponding Grignard reagents (at low temperature), they displayed full compatibility with various functional groups under the protic reaction conditions. Preliminary mechanistic studies including stoichiometric and catalytic reaction examination provided evidence to support the operation of the mechanism consisted of oxidative addition of deslyl chloride to Pd(0) and quick tautomerization to give a palladium enolate species II (ROPdCl), displacement of the enolate group in II by R2OH, followed by CO insertion to give alkoxycarbonyl palladium complex V, which undergoes transmetalation with R13ln and reductive elimination to afford the product and a Pd(0) species. In this mechanism, the alkoxycarbonyl group was transferred to the palladium center prior to the alkyl group, different from traditional ways initiated from oxidative addition of alkyl halides to a Pd(0) species.