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. 2016 Jul 8;21(7):897.
doi: 10.3390/molecules21070897.

Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄

Raffaella Mancuso  1 , Asif Maner  2 , Ida Ziccarelli  3 , Christian Pomelli  4 , Cinzia Chiappe  5 , Nicola Della Ca'  6 , Lucia Veltri  7 , Bartolo Gabriele  8
Affiliations

Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄

Raffaella Mancuso et al. Molecules. .

Abstract

A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

Keywords: carbonylation; cascade catalysis; oxazolidinones; palladium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
The concept of “auto-tandem catalysis; the same catalyst promotes the two concatenated catalytic cycles.
Scheme 2
Scheme 2
Auto-tandem catalysis leading to oxazolidinones 3 by sequential PdI2/KI-catalyzed oxidative monoaminocarbonylation of propargylic amines 1 to give 2-ynamide intermediates I followed by PdI2/KI-catalyzed and water-promoted oxidative cyclocarbonylation of I (anionic iodide ligands are omitted for clarity).
See this image and copyright information in PMC

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