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Palladium-Catalyzed C–H Functionalization of Acyldiazomethane and Tandem Cross-Coupling Reactions

Ye, Fei, Qu, Shuanglin, Zhou, Lei, Peng, Cheng, Wang, Chengpeng, Cheng, Jiajia, Hossain, Mohammad Lokman, Liu, Yizhou, Zhang, Yan, Wang, Zhi-Xiang, Wang, Jianbo
Journal of the American Chemical Society 2015 v.137 no.13 pp. 4435-4444
diazo compounds, energy, esters, extrusion, iodides, methodology, migratory behavior, nitrogen, palladium
Palladium-catalyzed C–H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd–carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd–EDA) complex is less favorable. The reaction instead proceeds through Ag₂CO₃ assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C–H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd–carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).