Journal article
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, Allan J Canty, Richard AJ O’Hair
Australian Journal of Chemistry: an international journal for chemical science | CSIRO Publishing | Published : 2023
DOI: 10.1071/ch23026
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 pallad..
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Awarded by University of Melbourne
Funding Acknowledgements
We thank Professor Uta Wille for access to the GC-MS. We thank Professor Jonathan White for the X-ray crystallographic structure determination of compound 25a (Supplementary Fig. S12, Supplementary Table S1). We thank the Bio21 Mass Spectrometry and Proteomics Facility for access to the ThermoScientific Exactive Plus Orbitrap mass spectrometer. YY thanks The University of Melbourne for the award of a PhD scholarship.