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Issue 44, 2016
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An MEDT study of the carbenoid-type [3 + 2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones

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Abstract

The molecular mechanism of the carbenoid-type [3 + 2] cycloaddition (32CA) reactions of a nitrile ylide (NY) with a non-chiral and a chiral oxazolidinone has been studied within Molecular Electron Density Theory (MEDT) at the MPWB1K/6-31G(d) computational level. Topological analysis of the Electron Localisation Function (ELF) of the NY shows that it presents a carbenoid structure. The high nucleophilic character of the NY together with the electrophilic character of the non-chiral oxazolidinone favour a polar 32CA reaction with a very low activation energy, the reaction being completely meta/endo selective. A Bonding Evolution Theory (BET) study of the molecular mechanism makes it possible to characterise a two-stage one-step carbenoid-type mechanism. Non-Covalent Interactions (NCI) analysis of the 32CA reaction between the NY and chiral oxazolidinone correctly explains the diastereoselectivity experimentally observed.

Graphical abstract: An MEDT study of the carbenoid-type [3 + 2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones

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Publication details

The article was received on 09 Sep 2016, accepted on 11 Oct 2016 and first published on 11 Oct 2016


Article type: Paper
DOI: 10.1039/C6OB01989G
Citation: Org. Biomol. Chem., 2016,14, 10427-10436
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    An MEDT study of the carbenoid-type [3 + 2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones

    L. R. Domingo, M. Ríos-Gutiérrez and P. Pérez, Org. Biomol. Chem., 2016, 14, 10427
    DOI: 10.1039/C6OB01989G

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