Palladium-mediated CO2 extrusion followed by insertion of ketenes: translating mechanistic studies to develop a one-pot method for the synthesis of ketones
Yang Yang
A , Allan J. Canty B and Richard A. J. O’Hair A *
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.
Abstract
Multistage mass spectrometry (MSn) experiments were used to explore extrusion–insertion (ExIn) reactions of the palladium complex [(phen)Pd(O2CPh)]+ (phen, 1,10-phenanthroline). Under collision-induced dissociation (CID) conditions, the organopalladium cation [(phen)Pd(Ph)]+ was formed via decarboxylation and was found to react with phenylmethylketene to yield the enolate [(phen)Pd(CPhMeC(O)Ph)]+ via an insertion reaction. A further stage of CID revealed that the enolate fragments via loss of styrene to form the acyl complex [(phen)Pd(C(O)Ph)]+. Formation of both the coordinated enolate and acyl anions is supported by density functional theory (DFT) calculations. Attempts to develop a palladium-mediated one-pot synthesis of ketones from 2,6-dimethoxybenzoic acid as the key substrate and the ketene substrates R1R2C═C═O (R1 = Ph, R2 = Me; R1 = R2 = Ph) proved challenging owing to low yields and side product formation.
Keywords: collision-induced dissociation, decarboxylation, DFT calculations, extrusion–insertion reactions, insertion of ketene, multistage mass spectrometry, palladium-mediated reactions, reaction mechanisms.
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