Journal article
Synthesis of Amidines by Palladium-Mediated CO 2 Extrusion Followed by Insertion of Carbodiimides: Translating Mechanistic Studies to Develop a One-Pot Method
Y Yang, A Noor, AJ Canty, A Ariafard, PS Donnelly, RAJ O'Hair
Organometallics | AMER CHEMICAL SOC | Published : 2019
Abstract
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 ..
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Awarded by Australian Research Council
Funding Acknowledgements
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.