The<scp>B</scp>aeyer‐<scp>V</scp>illigerOxidation of Aldehydes and Ketones

Hassall, C. H.

doi:10.1002/0471264180.or009.03

Cited by 20 publications

(9 citation statements)

References 117 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this section, we will show a cascade transformation of an alkyne that involves two “carbonyl reactions”, the Petasis-Ferrier reaction and an “aza Baeyer-Villiger (BV) rearrangement”. The Baeyer-Villiger reaction provides an important synthetic connection between ketones and esters [94,95,96,97,98,99]. More than a century after its discovery, this transformation still continues to provide a valuable connection between these key organic functional groups.…”

Section: The “Oxidant-free Nitrogen Baeyer-villiger Rearrangement”mentioning

confidence: 99%

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

et al. 2019

View full text Add to dashboard Cite

The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these “obvious” traits, there are other more subtle, often concealed aspects of this functional group’s appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, “classic carbonyl chemistry” can be accessed through alkynes, and new transformations can be engineered by unmasking the hidden carbonyl nature of alkynes. The goal of this review is to illustrate the advantages of using alkynes as an entry point to carbonyl reactions while highlighting reports from the literature where, sometimes without full appreciation, the concept of using alkynes as a hidden entry into carbonyl chemistry has been applied.

show abstract

Section: The “Oxidant-free Nitrogen Baeyer-villiger Rearrangement”mentioning

confidence: 99%

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

et al. 2019

View full text Add to dashboard Cite

show abstract

“…The BV reaction is the oxidation of ketones or aldehydes A under the action of hydrogen peroxide, hydroperoxides, Caro’s acid (H 2 SO 5 ), or organic peracids to yield esters, lactones, or carboxylic acids B ( Scheme 1 ) [ 190 – 191 ].…”

Section: Reviewmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

193

136

View full text Add to dashboard Cite

SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

show abstract

“…Hydrogen peroxide can be used if suitably activated by a catalyst, or in the presence of a strong acid, or even in alkaline conditions [33,34]. α-Diketones react readily with BV reagents: in inert solvents anhydrides are formed, while in alkaline or acidic media simple carboxylic acids are generally produced in good yields [35]. In 1930 Böeseken et al [36] prepared 9,10-diketostearic acid (11) by oxidation of 9-octadecynoic acid with 70% nitric acid at 10-25% yield and submitted it to the reaction with 15% excess peracetic acid in acetic acid for one day.…”

Section: Epoxidation Of Oleic Acidmentioning

confidence: 99%

Conversion of Oleic Acid into Azelaic and Pelargonic Acid by a Chemo-Enzymatic Route

Brenna

Colombo

Lecce³

et al. 2020

Molecules

View full text Add to dashboard Cite

A chemo-enzymatic approach for the conversion of oleic acid into azelaic and pelargonic acid is herein described. It represents a sustainable alternative to ozonolysis, currently employed at the industrial scale to perform the reaction. Azelaic acid is produced in high chemical purity in 44% isolation yield after three steps, avoiding column chromatography purifications. In the first step, the lipase-mediated generation of peroleic acid in the presence of 35% H2O2 is employed for the self-epoxidation of the unsaturated acid to the corresponding oxirane derivative. This intermediate is submitted to in situ acid-catalyzed opening, to afford 9,10-dihydroxystearic acid, which readily crystallizes from the reaction medium. The chemical oxidation of the diol derivative, using atmospheric oxygen as a stoichiometric oxidant with catalytic quantities of Fe(NO3)3∙9∙H2O, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and NaCl, affords 9,10-dioxostearic acid which is cleaved by the action of 35% H2O2 in mild conditions, without requiring any catalyst, to give pelargonic and azelaic acid.

show abstract

TheBaeyer‐VilligerOxidation of Aldehydes and Ketones

Cited by 20 publications

References 117 publications

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Rearrangements of organic peroxides and related processes

Conversion of Oleic Acid into Azelaic and Pelargonic Acid by a Chemo-Enzymatic Route

Contact Info

Product

Resources

About