Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 46, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202201153
Keywords
alkylation; carbanions; elimination; nitroarenes; sulfones
Categories
Funding
- SONATA BIS 3 program of the National Science Centre, Poland [DEC-2013/10/E/ST5/00030]
- Interdisciplinary Centre for Mathematical and Computational Modelling (ICM), University of Warsaw [G77-18]
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The alkylation of nitroarenes via Vicarious Nucleophilic Substitution (VNS) was experimentally tested and modeled with DFT calculations. Mechanistic studies showed intrinsic differences between the reactions of the carbanion precursor PhSO2CH2Cl and alkyl phenyl sulfones with benzenesulfinate as a leaving group. Steric hindrance developed at the beta-elimination step for the latter precursors, raising the energy barrier and resulting in the formation of byproducts.
Alkylation of nitroarenes via Vicarious Nucleophilic Substitution (VNS) was tested experimentally and modelled with DFT calculations. Mechanistic studies reveal intrinsic differences between reactions of archetypal carbanion precursor PhSO2CH2Cl, and alkyl phenyl sulfones, in which benzenesulfinate acts as a leaving group. Accordingly, for the latter precursors steric hindrance develops at the beta-elimination step, that raises energy barrier and results in the formation of byproducts.
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