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100 Years of Baeyer–Villiger Oxidations
Author(s) -
Renz Michael,
Meunier Bernard
Publication year - 1999
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199904)1999:4<737::aid-ejoc737>3.0.co;2-b
Subject(s) - chemistry , baeyer–villiger oxidation , benzophenone , peroxide , nucleophile , derivative (finance) , stereochemistry , organic chemistry , hydrogen peroxide , catalysis , financial economics , economics
In the present review, we report the discovery of the formation of esters and lactones by oxidation of ketones with a peroxide derivative, namely the Baeyer–Villiger reaction. This reaction was first reported by Adolf von Baeyer and Victor Villiger a century ago in 1899, just one year after the oxidant they used (KHSO 5 ) has been described. Furthermore, Baeyer and Villiger established the composition of this new inorganic peroxide and showed that its instability was the reason of a controversy between several European chemists between 1878 and 1893. For the first 50 years the mechanism of the Baeyer–Villiger reaction was a matter of debate. A side product, 1,2,4,5‐tetraoxocyclohexane, was ruled out as an intermediate in the ester formation by Dilthey. Criegee postulated a nucleophilic attack of the oxidant on the carbonyl group. This mechanism was confirmed by von E. Doering by a labeling experiment with [ 18 O]benzophenone. The rearrangement step occurs with retention of the stereochemistry at the migrating center. The competitive migration and the rate‐determining step are also discussed in this review.