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Bornemann H, Wentrup C. Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products. J Org Chem. 2005;70(15):5862-8doi: 10.1021/jo050429e.
Bornemann, H., & Wentrup, C. (2005). Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products. The Journal of organic chemistry, 70(15), 5862-8. https://doi.org/10.1021/jo050429e
Bornemann, Holger, and Wentrup, Curt. "Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products." The Journal of organic chemistry vol. 70,15 (2005): 5862-8. doi: https://doi.org/10.1021/jo050429e
Bornemann H, Wentrup C. Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products. J Org Chem. 2005 Jul 22;70(15):5862-8. doi: 10.1021/jo050429e. PMID: 16018679.
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J Org Chem. 2005 Jul 22;70(15):5862-8. doi: 10.1021/jo050429e.

Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products.

The Journal of organic chemistry

Holger Bornemann, Curt Wentrup

Affiliations

  1. Chemistry Building, School of Molecular and Microbial Sciences, The University of Queensland, Brisbane, Qld 4072, Australia.

PMID: 16018679 DOI: 10.1021/jo050429e

Abstract

The energy surface connecting oxazinium olates 9, several possible conformers of ketenes 10 and 11, and the final cyclization products 12, 13 and 14, as well as the isomeric 1,3-oxazine-6-ones 15, ring opening of the latter to N-acylimidoylketenes 16, and subsequent rearrangement of 16 to oxoketenimines 17, azetinones 18, and the cyclization products 19 and 20 are evaluated computationally at the B3LYP/6-31G and B3LYP/6-311+G//B3LYP/6-31G levels. The cyclizations of ketenes to oxazinium olates 9 and oxazines 15 have the characteristics of pseudopericyclic reactions. Plots of the energy vs internal reaction coordinate for the cyclization of transoid acylketenes such as 10 to 9 (via TS1) and 16 to 15 (via TS7) feature two inflection points and indicate that the part of the energy surface above the lower inflection points describe internal rotation of the acyl function in the ketene moiety, and the part below this point describes the cyclization of the cisoid ketene to the planar mesoionic oxazinium olate 9 or oxazinone 15. The 1,3-shifts of the OR group that interconvert ketenes 16 and ketenimines 17 via four-membered cyclic transition states TS8 behave similarly, the first portion (from the ketenimine side) of the activation barrier being due largely to internal rotation of substituents, and the top part being due to the 1,3-shift proper.

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