Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration
Yang Yang A , Allan J. Canty B and Richard A. J. O’Hair
A *
+ Author Affiliations
- Author Affiliations
A School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Vic. 3010, Australia.
B School of Natural Sciences - Chemistry, University of Tasmania, Private Bag 75, Hobart, Tas. 7001, Australia.
Australian Journal of Chemistry 76(1) 49-57 https://doi.org/10.1071/CH22209
Submitted: 27 September 2022 Accepted: 3 November 2022 Published: 16 December 2022
© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.
Abstract
The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl.
Keywords: biaryl coupling, desulfination, DFT calculations, extrusion, insertion, mass spectrometry, palladium mediated reactions, reaction mechanisms.
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