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A DFT/PCM-based methodology for predicting solvolytic reactivities of organic carbonates

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Abstract

The possibility of employing quantum mechanical computations to predict solvolysis rates of benzhydryl aryl/alkyl (Ar/R) carbonates and to determine nucleofugalities of various Ar/R carbonate leaving groups in terms of Nf values is examined. Since unassisted SN1 transition states of neutral substrates cannot be optimized by using implicit solvation models, a model reaction that includes anchimerically assisted heterolysis of 2-oxyethyl Ar/R carbonates is utilized to determine the relative reactivities of both benzhydryl Ar/R carbonate substrates and Ar/R carbonate leaving groups. Very good linear correlations have been obtained between activation free energies of the model reaction, calculated by using the M06-2X method in conjunction with the IEFPCM solvation model, and activation free energies in the literature for solvolysis of the corresponding benzhydryl Ar/R carbonates in a given solvent. The slopes of close to unity demonstrate that calculated and measured relative reactivities of the Ar/R carbonate leaving groups are practically the same. Very good agreement between experiment and theory has enabled extending the nucleofugality (Nf) scale established by Mayr and co-workers (Acc. Chem. Res., 2010, 43, 1537–1549) with numerous new Ar/R carbonate leaving groups.

Graphical abstract: A DFT/PCM-based methodology for predicting solvolytic reactivities of organic carbonates

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Publication details

The article was received on 18 Apr 2018, accepted on 30 May 2018 and first published on 11 Jun 2018


Article type: Paper
DOI: 10.1039/C8OB00917A
Citation: Org. Biomol. Chem., 2018, Advance Article
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    A DFT/PCM-based methodology for predicting solvolytic reactivities of organic carbonates

    M. Matić and B. Denegri, Org. Biomol. Chem., 2018, Advance Article , DOI: 10.1039/C8OB00917A

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