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Efficient methylation of anilines with methanol catalysed by cyclometalated ruthenium complexes

2021, Piehl, Patrick, Amuso, Roberta, Spannenberg, Anke, Gabriele, Bartolo, Neumann, Helfried, Beller, Matthias

Cyclometalated ruthenium complexes4-10allow the effective methylation of anilines with methanol to selectively giveN-methylanilines. This hydrogen autotransfer procedure proceeds under mild conditions (60 °C) in a practical manner (NaOH as base). Mechanistic investigations suggest an active homogenous ruthenium complex and β-hydride elimination of methanol as the rate determining step. © The Royal Society of Chemistry 2021.

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A general strategy for the synthesis of α-trifluoromethyl- and α-perfluoroalkyl-β-lactams via palladium-catalyzed carbonylation

2021, Li, Yang, Zhang, Cai-Lin, Huang, Wei-Heng, Sun, Ning, Hao, Meng, Neumann, Helfried, Beller, Matthias

β-Lactam compounds play a key role in medicinal chemistry, specifically as the most important class of antibiotics. Here, we report a novel one-step approach for the synthesis of α-(trifluoromethyl)-β-lactams and related products from fluorinated olefins, anilines and CO. Utilization of an advanced palladium catalyst system with the Ruphos ligand allows for selective cycloaminocarbonylations to give diverse fluorinated β-lactams in high yields. © The Royal Society of Chemistry 2021.