Advanced Topic 873 of 1102 Organic Chemistry
Baeyer-Villiger Oxidation
Ketones are converted to esters by peracids.
In-depth explanation of Baeyer-Villiger Oxidation
The Baeyer-Villiger oxidation converts a ketone into an ester, or a cyclic ketone into a lactone, by inserting an oxygen atom next to the carbonyl group. The reagent is a peracid, such as meta-chloroperbenzoic acid, which attacks the carbonyl carbon to form a tetrahedral intermediate. A group on the carbon migrates to oxygen with its bonding electrons, and the group that migrates best is the one better able to stabilize positive charge, typically a tertiary alkyl or secondary alkyl group over a methyl. The migration is stereospecific and retains configuration at the migrating carbon.
Going deeper: Baeyer-Villiger Oxidation
Key ideas: Ketone plus peracid (mCPBA or peracetic acid) inserts an oxygen next to the carbonyl, giving an ester (or lactone from cyclic ketones). Migratory aptitude of the group moving to oxygen: tertiary > cyclohexyl > secondary > phenyl > primary > methyl. Retention of configuration at the migrating carbon. Cyclohexanone gives caprolactone; acetophenone gives phenyl acetate.
Common mistakes and connections: Students place the oxygen on the wrong side by misjudging migratory aptitude, for instance moving methyl before phenyl. Another error is thinking the carbonyl oxygen is replaced; a new oxygen is inserted. Links to Criegee intermediate, rearrangements to electron-deficient oxygen and hydroperoxide chemistry.
Visualization of Baeyer-Villiger Oxidation
In the Baeyer-Villiger oxidation the more substituted group migrates to oxygen: tertiary > secondary > phenyl > primary > methyl. The interactive lesson shows this as a live animation or chart.
Worked example and use case
Cyclohexanone is converted by peracid into caprolactone, a cyclic ester formed by inserting oxygen into the ring.
Frequently asked questions about Baeyer-Villiger Oxidation
What is Baeyer-Villiger Oxidation?
Ketones are converted to esters by peracids.
Is Baeyer-Villiger Oxidation a beginner, intermediate or advanced topic?
Baeyer-Villiger Oxidation is a advanced topic in Organic Chemistry. It builds on beginner and intermediate topics, so review those first if needed.
What should I learn before Baeyer-Villiger Oxidation?
Study these earlier topics in Organic Chemistry first: Epoxides, Sharpless Epoxidation, Hydroboration-Oxidation.
What comes after Baeyer-Villiger Oxidation?
The next topics in Organic Chemistry are Beckmann Rearrangement and Pinacol Rearrangement.
Can I practise Baeyer-Villiger Oxidation with quizzes?
Yes. The interactive lesson includes a self-check question on Baeyer-Villiger Oxidation, and the Organic Chemistry quiz draws on every topic in this area.
Where Baeyer-Villiger Oxidation fits in Organic Chemistry
Baeyer-Villiger Oxidation is topic 145 of 148 in Organic Chemistry.