TheBaeyer–VilligerOxidation of Ketones and Aldehydes

Abstract

The oxidative conversion of alicyclic ketones into lactones with permonosulfuric acid was discovered by Baeyer and Villiger in 1899, and in their honor the general process by which ketones are converted into esters or lactones is now known as the Baeyer–Villiger reaction. The literature on this synthetically useful process has been reviewed comprehensively through 1953 in Volume 9 of Organic Reactions , and less comprehensive reviews of the reaction have appeared since then. More recent investigations have led to the development of new synthetic reagents, to improvements in experimental reaction conditions, and to a better understanding of regiochemical and stereochemical aspects of the reaction. Baeyer–Villiger reactions now often can be carried out with functional group chemoselectivity and regiochemical control. Although the recent removal from commerce of 90% hydrogen peroxide and reagents based upon this oxidant are a setback to Baeyer–Villiger reaction methodology, alternative reagents, catalysts, and methods described in this review are available to fill the gaps. The definition of the Baeyer–Villiger reaction is somewhat fuzzy, and can be considered to include both ketones and aldehydes. In addition to the traditional use of organic and inorganic peracids as oxidants, examples of oxygen insertion reactions using hydrogen peroxide, alkyl peroxides, and several metal ion oxidants are considered to fall within the scope of this chapter and are included in the tabular survey.

Baeyer−Villiger Monooxygenases: More Than Just Green Chemistry

“…An earlier review by Krow highlights the wide-ranging applications of this transformation, from the synthesis of steroids, antibiotics, and pheromones to the synthesis of monomers for polymerization. 4 Now almost a century and a dozen years later, the development of the BV reaction is still going strong marked by quests for oxidants that are more chemoselective and efficient, 5 catalysis with transition metal complexes, and also the use of ionic liquids. 6 On the chemical aspects of BV oxidations, readers are referred to several key recent reviews.…”

Design and Synthesis of C-Ring Lactone- and Lactam-Based Podophyllotoxin Analogues as Anticancer Agents

“…However, the requirement of lactone ring cannot be ruled out. There was no significant difference in the cytotoxicity on converting lactone moiety to lactam (12,18). The inclusion of nitrogen atom in ring C was not beneficial due to insufficient bulkiness, which otherwise is required for better activity at C-4 position of PDT analogues.…”

“…On alkaline hydrolysis, 8 yielded 3,4-methylenedioxyphenol (6) in 95% yield. 6 was stirred with 3,4,5-trimethoxycinnamic acid methyl ester (10a) in trifluoroacetic acid at room temperature for 24 h to produce the desired product (12) in 34% yield. 13) Similarly, various other phenols such as 3-methoxyphenol, 3,5-dimethoxyphenol, 3,4-dimethoxyphenol, 6-methoxy-2-naphthol, and estrone were used to produce the corresponding neoflavonoids (24-28).…”

Trifuoroperacetic acid in consecutive Criegee rearrangement and carboxonium ions generation

“…Numerous reviews described the synthetic and mechanistic aspects of the Baeyer-Villiger reaction 2,3,17,18 and Criegee rearrangement, 9,12,19 but none have focused their attention on the consecutive Criegee rearrangement (Scheme 2). Research activity during the last ten years, however, has led to new synthetic applications of consecutive Criegee rearrangements that certainly warrant the need of the present review.…”

“…2,3 The treatment of aldehydes or ketones 1 with peracids always leads to the formation of hydroxyperesters 2 ("Criegee intermediate"). 4 A consequent rearrangement of hydroxyperesters 2 leads to ester 3 as the final product.…”