A DFT/PCM-based methodology for predicting solvolytic reactivities of organic carbonates
Literature Information
Mirela Matić, Bernard Denegri
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.
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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.




