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Uncertainty Quantification of Reactivity Scales.

ABSTRACT: According to Mayr, polar organic synthesis can be rationalized by a simple empirical relationship linking bimolecular rate constants to as few as three reactivity parameters. Here, we propose an extension to Mayr's reactivity method that is rooted in uncertainty quantification and transforms the reactivity parameters into probability distributions. Through uncertainty propagation, these distributions can be transformed into uncertainty estimates for bimolecular rate constants. Chemists can exploit these virtual error bars to enhance synthesis planning and to decrease the ambiguity of conclusions drawn from experimental data. We demonstrate the above at the example of the reference data set released by Mayr and co-workers [J. Am. Chem. Soc. 2001, 123, 9500; J. Am. Chem. Soc. 2012, 134, 13902]. As by-product of the new approach, we obtain revised reactivity parameters for 36 π-nucleophiles and 32 benzhydrylium ions.

SUBMITTER: Proppe J

PROVIDER: S-EPMC9314972 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Uncertainty Quantification of Reactivity Scales.

Proppe Jonny J Kircher Johannes J

Chemphyschem : a European journal of chemical physics and physical chemistry 20220318 8

According to Mayr, polar organic synthesis can be rationalized by a simple empirical relationship linking bimolecular rate constants to as few as three reactivity parameters. Here, we propose an extension to Mayr's reactivity method that is rooted in uncertainty quantification and transforms the reactivity parameters into probability distributions. Through uncertainty propagation, these distributions can be transformed into uncertainty estimates for bimolecular rate constants. Chemists can explo ...[more]

PMID: 35189024

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Dataset Information

Uncertainty Quantification of Reactivity Scales.

Publications

Uncertainty Quantification of Reactivity Scales.

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