Synthesis of 2-Alkynoates by Palladium(II)-Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols

Qun Cao; N Louise Hughes; Mark J Muldoon

doi:10.1002/chem.201602558

Synthesis of 2-Alkynoates by Palladium(II)-Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols

Chemistry. 2016 Aug 16;22(34):11982-5. doi: 10.1002/chem.201602558. Epub 2016 Jul 19.

Authors

Qun Cao¹, N Louise Hughes¹, Mark J Muldoon²

Affiliations

¹ School of Chemistry and Chemical Engineering, Queen's University Belfast, Stranmillis Road, Belfast, BT9 5AG, Northern Ireland.
² School of Chemistry and Chemical Engineering, Queen's University Belfast, Stranmillis Road, Belfast, BT9 5AG, Northern Ireland. m.j.muldoon@qub.ac.uk.

Abstract

A homogeneous Pd(II) catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2-alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures.

Keywords: alkynes; carbonylation; homogeneous catalysis; oxidation; palladium.