Oxidative Ring Enlargement of Cyclic Ketones by Peroxytrifluoroacetic Acid<sup>1</sup>

Sager, W. F.; Duckworth, Alan C.

doi:10.1021/ja01606a067

Cited by 38 publications

(8 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Sager and Duckworth explained the enhanced reaction rates by the shows that the oxidation of ketone 1j proceeds significantly slower than that of ketone 1i in which the carbonyl group fact that strong acids are better leaving groups than weak ones and should speed up the reaction. [93] However, a rate-been reviewed by Krow.…”

Section: The Kinetics Of the Baeyer؊villiger Reactionmentioning

confidence: 99%

100 Years of Baeyer–Villiger Oxidations

Renz

Meunier²

1999

Eur. J. Org. Chem.

543

307

View full text Add to dashboard Cite

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 (KHSO5) 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 [18O]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.

show abstract

Section: The Kinetics Of the Baeyer؊villiger Reactionmentioning

confidence: 99%

100 Years of Baeyer–Villiger Oxidations

Renz

Meunier²

1999

Eur. J. Org. Chem.

543

307

View full text Add to dashboard Cite

show abstract

“…This reagent is very selective, and is especially suited for converting primary amines to nitro compounds (605), and olefins to epoxides [606) and trans-diols (after hydrolysis of the unstable intermediates, vicinal hydroxytrifluoroacetates) [607), and ideal for converting ketones to esters in the Baeyer-Villiger reaction. The latter reaction is important not only from the synthetic point of view [608,609), but also for theoretical studies of migratory aptitudes of various groups (610) ( Table 51). …”

Section: %mentioning

confidence: 99%

Organic Fluorine Chemistry

Hudlický

1971

View full text Add to dashboard Cite

“…The B-V reactions is commonly performed utilizing peracids as oxidants, including trifluoroperacetic acid [6], perbenzoic acid [7], m-chloroperbenzoic acid [2]. However, these oxidants not only contain low effective oxygen contents [8], but also are potentially explosive [9].…”

Section: Introductionmentioning

confidence: 99%