Synthesis of Amidines by Palladium-Mediated CO2 Extrusion Followed by Insertion of Carbodiimides: Translating Mechanistic Studies to Develop a One-Pot Method
Yang Yang, Asif Noor, Allan J Canty, Alireza Ariafard, Paul S Donnelly, Richard AJ O'Hair
ORGANOMETALLICS | AMER CHEMICAL SOC | Published : 2019
A palladium-mediated one-pot synthesis of amidines from aromatic carboxylic acids and carbodiimides (RNCNR) is reported as an isoelectronic adaption of CO 2 ExIn (ExIn = Extrusion-Insertion) reactions developed for the synthesis of thioamides from carboxylic acids and isothiocyanates (RNCS). Multistage mass spectrometry (MS n ) experiments for model systems established "proof of concept", demonstrating decarboxylation of [(L)Pd(O 2 CAr)] + (L = 1,10-phenanthroline or py), to give [(L)PdAr] + , followed by reaction with a carbodiimide, RNCNR, to yield [(L)Pd(NRC(NR)Ar)] + (R = isopropyl). DFT calculations predicted these reactions as highly exothermic and occurring via carbodiimide insertion ..View full abstract
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Awarded by ARC
A.J.C., P.S.D., and R.A.J.O. thank the ARC for funding (DP180101187), and the National Computing Infrastructure. We thank the Bio21 Mass Spectrometry and Proteomics Facility for access to the Thermo OrbiTrap Fusion Lumos mass spectrometer.