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Theoretical studies of five-membered ring ketene acetals

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Abstract

Cyclic ketene acetals are a class of organic molecules characterized by a nucleophilic exo-methylene carbon attached to a carbon with two adjacent O, N, or S atoms. We have carried out a systematic computational study of a series of five-membered cyclic acetals like 2-methylene-1,3-dioxolane and its OS, SS, NO, NS, and NN analogs as well as all the protonated species. The calculations were performed at the MP2 level using a triple zeta plus polarization basis set. The nucleophilicity was discussed in terms of geometrical factors, calculated atomic charges, calculated chemical shifts, and proton affinities. All the six neutral species were strong nucleophiles. The NN analog was predicted to be the strongest and the SS analog the weakest nucleophile.

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Authors and Affiliations

  1. Department of Chemistry, Mississippi State University, PO-Box 9573, Mississippi State, MS, 39762, USA

    Debbie J. Beard, Chandler R. Pace, Charles U. Pittman Jr. & Svein Saebø

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  1. Debbie J. Beard
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  2. Chandler R. Pace
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  3. Charles U. Pittman Jr.
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  4. Svein Saebø
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Correspondence to Svein Saebø.

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Beard, D.J., Pace, C.R., Pittman, C.U. et al. Theoretical studies of five-membered ring ketene acetals. Struct Chem 20, 961–967 (2009). https://doi.org/10.1007/s11224-009-9496-y

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  • DOI: https://doi.org/10.1007/s11224-009-9496-y

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