Issue 31, 2012
From the journal:

Organic & Biomolecular Chemistry

Theoretical study on the hypervalent λ3-bromane strategy for Baeyer–Villiger oxidation of benzaldehyde and acetaldehyde: rearrangement mechanism†

Hui Fu,*ab   Shouwen Xie,b   Aiping Fu,c   Xufeng Lin,ab   Hui Zhaoa  and  Tianxu Yeb  

* Corresponding authors

a State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Shandong, Qingdao, People's Republic of China
E-mail: fuhui@upc.edu.cn

b College of Science, China University of Petroleum, Shandong, Qingdao, People's Republic of China

c Laboratory of New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, Qingdao University, Shandong, Qingdao, People's Republic of China

Abstract

The rearrangement mechanisms of the novel Baeyer–Villiger oxidation (BVO) of benzaldehyde and acetaldehyde have been studied using density functional theory methods. All structures associated with the product formation step of the new Criegee intermediate, α-hydroxyalkoxy-λ3-bromane, are reported. B3LYP/6-31++G** calculations give a good description for the group shift of these two typical reactants: phenyl shift is easier than hydrogen shift for benzaldehyde; hydrogen migration is more favorable than methyl migration for acetaldehyde. Different mechanisms and various conformers of the novel BVO reaction have been considered for the migration step. Solvent effects and rate constants are also taken into account. The calculated and experimentally observed branching ratios are in good agreement with each other.

Graphical abstract: Theoretical study on the hypervalent λ3-bromane strategy for Baeyer–Villiger oxidation of benzaldehyde and acetaldehyde: rearrangement mechanism

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Article information

DOI
https://doi.org/10.1039/C2OB25551K
Article type
Paper
Submitted
14 Mar 2012
Accepted
08 Jun 2012
First published
13 Jun 2012

Org. Biomol. Chem., 2012,10, 6333-6340

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Theoretical study on the hypervalent λ3-bromane strategy for Baeyer–Villiger oxidation of benzaldehyde and acetaldehyde: rearrangement mechanism

H. Fu, S. Xie, A. Fu, X. Lin, H. Zhao and T. Ye, Org. Biomol. Chem., 2012, 10, 6333 DOI: 10.1039/C2OB25551K

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