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A theoretical study of the uncatalyzed and BF3-assisted Baeyer-Villiger reactions
KTH, Superseded Departments, Chemistry.ORCID iD: 0000-0003-2673-075X
2001 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 66, no 4, 1193-1199 p.Article in journal (Refereed) Published
Abstract [en]

The mechanisms for the uncatalyzed and boron trifluoride (BF3) assisted Baeyer-Villiger reactions between acetone and hydrogen peroxide have been investigated using high level ab initio [MP2 and CCSD(T)] and density functional theory (B3LYP) methods. Both steps in the uncatalyzed reaction are found to have very high transition state energies. It is clear that detectable amounts of the Crieege intermediate or the products cannot be formed without the aid of a catalyst. The main function of BF3 in both the addition step and the rearrangement (migration) step is to facilitate proton transfer. In the addition step the complexation of hydrogen peroxide with BF3 leads to an increased acidity of the attacking OH group, while in the rearrangement step BF3 takes active part in the proton-transfer process. This latter step is found to be rate determining with an activation free energy of 17.7 kcal/mol in organic solution. The products of the reaction are BF2OH, hydrogen fluoride, and methyl acetate. Thus, BF3 is not directly regenerated from the reaction.

Place, publisher, year, edition, pages
2001. Vol. 66, no 4, 1193-1199 p.
Keyword [en]
density-functional theory, basis-set requirements, ab-initio, exact exchange, rearrangement, oxidations, energies, molecules, binding, model
URN: urn:nbn:se:kth:diva-20376DOI: 10.1021/jo001278cISI: 000167049700017OAI: diva2:339071
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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