page_title: Baeyer–Villiger oxidation
section_title: Historical background
hierarchical_section_title: Baeyer–Villiger oxidation / Historical background
caption_attribution_description: English: Proposed Baeyer Villiger Intermediates
context_page_description: The Baeyer–Villiger oxidation is an organic reaction that forms an ester from a ketone or a lactone from a cyclic ketone, using peroxyacids or peroxides as the oxidant. The reaction is named after Adolf von Baeyer and Victor Villiger who first reported the reaction in 1899.
context_section_description: In 1899, Adolf Baeyer and Victor Villiger first published a demonstration of the reaction that we now know as the Baeyer–Villiger oxidation. They used peroxymonosulfuric acid to make the corresponding lactones from camphor, menthone, and tetrahydrocarvone.
  There were three suggested reaction mechanisms of the Baeyer–Villiger oxidation that seemed to fit with observed reaction outcomes. These three reaction mechanisms can really be split into two pathways of peroxyacid attack - on either the oxygen or the carbon of the carbonyl group. Attack on oxygen could lead to two possible intermediates: Baeyer and Villiger suggested a dioxirane intermediate, while Georg Wittig and Gustav Pieper suggested a peroxide with no dioxirane formation. Carbon attack was suggested by Rudolf Criegee. In this pathway, the peracid attacks the carbonyl carbon, producing what is now known as the Criegee intermediate.
  In 1953, William von Eggers Doering and Edwin Dorfman elucidated the correct pathway for the reaction mechanism of the Baeyer–Villiger oxidation by using oxygen-18-labelling of benzophenone. The three different mechanisms would each lead to a different distribution of labelled products. The Criegee intermediate would lead to a product only labelled on the carbonyl oxygen. The product of the Wittig and Pieper intermediate is only labeled on the alkoxy group of the ester. The Baeyer and Villiger intermediate leads to a 1:1 distribution of both of the above products. The outcome of the labelling experiment supported the Criegee intermediate, which is now the generally accepted pathway.
caption: Proposed Baeyer-Villiger oxidation intermediates
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