Journal article

Palladium-Mediated CO2Extrusion Followed by Insertion of Allenes: Translating Mechanistic Studies to Develop a One-Pot Method for the Synthesis of Alkenes

Y Yang, B Spyrou, JM White, AJ Canty, PS Donnelly, RAJ O'Hair

Organometallics | Published : 2022

Abstract

A palladium-mediated one-pot synthesis of alkenes from aromatic carboxylic acids and allene substrates (R1R2C═C═CH2, where either: R1= Ph, R2= H; R1= Ph, R2= Me or R1= nPe, R2= H) is reported. This is an isoelectronic variant of CO2extrusion-insertion (ExIn) reactions previously developed using heterocumulenes for the synthesis of thioamides (from isothiocyanates, RNCS), amidines (from carbodiimides, RNCNR), and amides (from isocyanates, RNCO). Evidence that the key aryl-palladium intermediate reacts to form a stable allyl-palladium product via insertion of the allene at the C2 position that enables the synthesis of alkenes was provided by a combination of gas-phase multistage mass spectrome..

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Grants

Awarded by Australian Research Council


Funding Acknowledgements

The authors acknowledge the fi nancial support of the ARC (DP180101187 funding to A.J.C., P.D., and R.A.J.O.) . DFT calculations were carried out using the HPC facility of the University of Melbourne and the generous allocation of CPU from the National Computing Infrastructure. Y.Y. thanks the Australian Government for a Research Training Program (RTP) scholarship.