Baeyer-Villiger Oxidation
Introduction
Baeyer-Villiger oxidation reaction is a reaction in which hydrogen peroxide, m-chloroperoxybenzoic acid (m-CPBA), peracetic acid, or peroxytrifluoroacetic acid are used as oxidants to break the C-C bond of carbonyl groups, thereby introducing oxygen atoms, and oxidizing aldehydes and ketones to esters. 1 This reaction was first discovered by Adolf von Baeyer and Victor Villiger in 1899 when they studied the cracking of cyclic ketones.
The important characteristic of Baeyer-Villiger oxidation is that the stereochemistry of the migrating groups remains unchanged and the reaction has a certain regioselectivity. Regional specificity is the essence of this reaction, and groups with strong electron giving ability (replacing more carbon) preferentially migrate. The general migration order is: tertiary carbon > cyclohexyl > secondary carbon > benzyl > phenyl > primary carbon > methyl. Therefore, it has important significance for functional group conversion and ring expansion in organic synthesis.
Figure 1. Baeyer-Villiger oxidation reaction
Figure 2. Synthesis of lactones (cyclic esters) by oxidation of cyclones by Baeyer-Villiger
Mechanism
In the first step, the carbonyl group is protonated to increase its electrophilicity, and then peroxy acid is added to the cationic material to form the so-called Criegee intermediate (adduct).
Figure 3. Baeyer-Villiger oxidation reaction mechanism 1
When the carboxylic acid leaves the intermediate, it forms an electron deficient oxygen substituent, which immediately undergoes alkyl migration. This alkyl migration and the loss of carboxylic acids occur in a synergistic process. It is assumed that the migration group must be located opposite the broken oxygen oxygen single bond of the peroxide.
Figure 4. Baeyer-Villiger oxidation reaction mechanism 2
APPLICATION
1. The enzymatic Baeyer-Villiger oxidation: enantioselective synthesis of lactones from mesomeric cyclohexanones.2
2. Indole-2-carboxylates are converted in good yields to 3-hydroxyindole-2-carboxylates by use of a Baeyer–Villiger reaction sequence. A systematic examination of the various indole substituents revealed this route to be general in scope.3
3. [18F]Fluorophenols from non-activated [18F]fluorobenzaldehydes by Baeyer-Villiger oxidation.4
4. Baeyer-Villiger oxidation could be used to prepare dihydroxy derivative of dibenzo-18-crown-6 through acetylation of dibenzo-18-crown-6 followed by Baeyer-Villiger oxidation. The Baeyer-Villiger oxidation could be substantially accelerated using trifluoroacetic acid.5
5. A one-pot chemoenzymatic method has been described for the synthesis of γ-butyrolactones starting from the corresponding ketones through a Baeyer–Villiger reaction. 6
6. General metal-free Baeyer-Villiger type synthesis of vinyl acetates. Oxone, a oxidizing reagent, transforms α,β-unsaturated ketones of defined stereochemistry into their corresponding vinyl acetates through a Baeyer-Villiger reaction.7
RECENT RESEARCH AND TRENDS
1. The Baeyer-Villiger oxidation of cyclic ketones to the corresponding lactones using aqueous hydrogen peroxide as an oxidant over transition metal oxides was investigated.8
2. Silica-supported tricobalt tetraoxide (Co3O4/SiO2) catalysts prepared by the impregnation approach with different cobalt loadings were evaluated in the Baeyer–Villiger oxidation of cyclohexanone under Mukaiyama conditions. The application of Co3O4/SiO2 catalyst in oxidation of cyclohexanone is promising due to its relatively low-cost, high efficiency and excellent stability.9
3. Submicrometer-sized tin-containing MCM-41 particles with a size of several hundred nanometers(Sn-MCM-41/SMPs) were rapidly prepared with tin chloride as tin source and tetraethyl orthosilicate as silicon source via a dilute solution route in sodium hydroxide medium at room temperature.The material proved to be active and selective for Baeyer-Villiger oxidation of adamantanone with aqueous H2O2. The study shows that decreasing particle size of MCM-41 in submicrometer scale is an effective way to achieve catalysts for Baeyer-Villiger oxidations with improved catalytic performance.10
4. A new method for the chemo-enzymatic Baeyer–Villiger oxidation of cyclic ketones to lactones has been developed. Using the oxidation of cyclohexanone and cyclobutanone catalyzed by Candida antarctica lipase B or Novozyme-435 suspended in ionic liquids, the reaction rate and yield were improved.11
5. A kinetic resolution of racemic 2-substituted cyclopentanones via highly regio- and enantioselective Baeyer–Villiger oxidation has been successfully developed. 12
Reference
1.Yachnin BJ, Sprules T, McEvoy MB, Lau PCK, Berghuis AM. 2012. The Substrate-Bound Crystal Structure of a Baeyer?Villiger Monooxygenase Exhibits a Criegee-like Conformation. J. Am. Chem. Soc.. 134(18):7788-7795. https://doi.org/10.1021/ja211876p
2.Taschner MJ, Black DJ. 1988. The enzymatic Baeyer-Villiger oxidation: enantioselective synthesis of lactones from mesomeric cyclohexanones. J. Am. Chem. Soc.. 110(20):6892-6893. https://doi.org/10.1021/ja00228a053
3.Hickman ZL, Sturino CF, Lachance N. 2000. A concise synthesis of 3-hydroxyindole-2-carboxylates by a modified Baeyer?Villiger oxidation. Tetrahedron Letters. 41(43):8217-8220. https://doi.org/10.1016/s0040-4039(00)01456-8
4.Castillo Meleán J, Ermert J, Coenen H. 2014. [18F]Fluorophenols from non-activated [18F]fluorobenzaldehydes by Baeyer-Villiger oxidation. J Nucl Med. 55(1):155.
5.Utekar DR, Saman SD. 2014. Application of Bayer-Villiger Reaction to the Synthesis of Dibenzo-18-crown-6, Dibenzo-21-crown-7 and Dihydroxydibenzo-18-crown-6. Journal of the Korean Chemical Society. 58(2):193-197. https://doi.org/10.5012/jkcs.2014.58.2.193
6.González-Martínez D, Rodríguez-Mata M, Méndez-Sánchez D, Gotor V, Gotor-Fernández V. 2015. Lactonization reactions through hydrolase-catalyzed peracid formation.Use of lipases for chemoenzymatic Baeyer?Villiger oxidations of cyclobutanones. Journal of Molecular Catalysis B: Enzymatic. 11431-36. https://doi.org/10.1016/j.molcatb.2014.09.002
7.Poladura B, Martínez-Castañeda &, Rodríguez-Solla H, Llavona R, Concellón C, del Amo V. 2013. General Metal-Free Baeyer?Villiger-Type Synthesis of Vinyl Acetates. Org.Lett.. 15(11):2810-2813. https://doi.org/10.1021/ol401143q
8.Ma Q, Xing W, Xu J, Peng X. 2014. Baeyer?Villiger oxidation of cyclic ketones with aqueous hydrogen peroxide catalyzed by transition metal oxides. Catalysis Communications. 535-8. https://doi.org/10.1016/j.catcom.2014.04.017
9.Zang J, Ding Y, Pei Y, Liu J, Lin R, Yan L, Liu T, Lu Y. 2014. Efficient Co3O4/SiO2 catalyst for the Baeyer?Villiger oxidation of cyclohexanone. Reac Kinet Mech Cat. 112(1):159-171. https://doi.org/10.1007/s11144-014-0687-1
10.Chen N, Jiang Y, Cheng W, Lin K, Xu X. 2015. Synthesis of submicrometer-sized Sn-MCM-41 particles and their catalytic performance in Baeyer-Villiger oxidation. Chem. Res. Chin.Univ.. 31(1):138-143. https://doi.org/10.1007/s40242-014-4204-x
11.Drod A, Erfurt K, Bielas R, Chrobok A. Chemo-enzymatic Baeyer-Villiger oxidation in the presence of Candida antarctica lipase B and ionic liquids. New J. Chem.. 39(2):1315-1321. https://doi.org/10.1039/c4nj01976h
12.Zhou L, Liu X, Ji J, Zhang Y, Wu W, Liu Y, Lin L, Feng X. 2014. Regio- and Enantioselective Baeyer?Villiger Oxidation: Kinetic Resolution of Racemic 2-Substituted Cyclopentanones. Org.Lett.. 16(15):3938-3941. https://doi.org/10.1021/ol501737a