Nucleophilic substitution at the alkenyl and cyclopropyl carbon atoms of magnesium carbenoids: a DFT study

The results of DFT calculations demonstrated that the activation free energies for the nucleophilic substitution of (1-chlorovinyl)- and (1-chlorocyclopropyl)magnesium chlorides with a chloride ion were lower than those of chloroethene and chlorocyclopropane by 8.1 and 4.4kcal/mol, respectively, whi...

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Bibliographic Details
Published in:Tetrahedron letters 2013-09, Vol.54 (37), p.5072-5074
Main Authors: Kimura, Tsutomu, Satoh, Tsuyoshi
Format: Article
Language:English
Subjects:
1,2-Migration
Activation energy
Anions
Carbon
Chlorides
DFT calculation
Free energy
Magnesium
Magnesium carbenoid
Mathematical analysis
Nuclei
Nucleophilic substitution
SNV reaction
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Summary:The results of DFT calculations demonstrated that the activation free energies for the nucleophilic substitution of (1-chlorovinyl)- and (1-chlorocyclopropyl)magnesium chlorides with a chloride ion were lower than those of chloroethene and chlorocyclopropane by 8.1 and 4.4kcal/mol, respectively, which suggests that the magnesium atom on the electrophilic carbon atom facilitates nucleophilic substitution. The activation energies for the nucleophilic substitution of (1-chlorovinyl)magnesium chloride with methyl anion, vinyl anion, and acetylide ion via the 1,2-migration were calculated to be 21.3–23.2kcal/mol.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2013.07.030