Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant

Yusuke Izawa, Isao Shimizu, Akio Yamamoto

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.

Original languageEnglish
Pages (from-to)2033-2045
Number of pages13
JournalBulletin of the Chemical Society of Japan
Volume77
Issue number11
DOIs
Publication statusPublished - 2004

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Carbonylation
phosphine
Alkynes
Molecular oxygen
Palladium
Oxidants
Catalysts
Carbon Monoxide
Atmospheric pressure
Alcohols
Ions
Ligands
Oxidation
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant. / Izawa, Yusuke; Shimizu, Isao; Yamamoto, Akio.

In: Bulletin of the Chemical Society of Japan, Vol. 77, No. 11, 2004, p. 2033-2045.

Research output: Contribution to journalArticle

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