Reactions of dienes with selenium dioxide III. Selenolabdanes from methyl 15-O-Acetylisocupressate

Medarde, Manuel; Lopez, J. L.; Iribar, Josune; Feliciano, Arturo San; Carpy, A.; Léger, Jean‐Michel

doi:10.1016/0040-4020(95)00656-s

Cited by 8 publications

(3 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Selenium dioxide is a versatile oxidizing reagent in organic chemistry and is commonly used to convert allylic C–H bonds to the corresponding allylic alcohols or α,β-unsaturated carbonyl compounds, − though a variety of organic molecules undergo dehydrogenation (Scheme ). , The generally accepted mechanism of this allylic hydroxylation, proposed by Sharpless, starts with an electrophilic ene reaction followed by a [2,3] sigmatropic rearrangement leading to an intermediate seleninic acid . Further conversion of this intermediate leads to alcohol and ketone products as well as elemental selenium.…”

Section: Section Iii: Preparation Structure and Reactivity Patterns O...mentioning

confidence: 99%

Conversion Reactions of Cadmium Chalcogenide Nanocrystal Precursors

et al. 2013

View full text Add to dashboard Cite

Section: Section Iii: Preparation Structure and Reactivity Patterns O...mentioning

confidence: 99%

Conversion Reactions of Cadmium Chalcogenide Nanocrystal Precursors

et al. 2013

View full text Add to dashboard Cite

“…In alcohols selenic( IV ) esters are formed in situ, e.g. dimethyl selenate( IV ) postulated for the reaction carried in methanol 9. Although this ester was never isolated, the stable diethyl analogue was successfully used for oxidation of some organophosphorus compounds and fenacyl halides 1e.…”

Section: Selenium and Its Inorganic Compoundsmentioning

confidence: 99%

“…This reaction, carried out in methanol, was applied for α‐hydroxylation of natural 1,6‐dienes (among them linalol and its acetate) and 15‐ O ‐acetylisocupressone. Other solvents such as dioxane and formic acid were also used but in the second case formates of the corresponding allyl alcohols were produced 9,11.…”

Section: Selenium and Its Inorganic Compoundsmentioning

confidence: 99%

Selenium‐Promoted Oxidation of Organic Compounds: Reactions and Mechanisms

et al. 2003

View full text Add to dashboard Cite

Oxidation reactions are fundamental processes widely applied in organic synthesis. Elemental selenium and more often its compounds have been successfully used as stoichiometric reagents and catalysts for oxidation of different organic substrates. Selenium(IV) oxide, areneseleninic acids and their anhydrides are widely used as stoichiometric oxidants or as oxygen‐transfer agents for oxygen donors, particularly hydrogen peroxide and tert‐butyl hydroperoxide. Organic diselenides (the precursors of seleninic acids) have been used as oxidation catalysts while dimethyl and diphenyl selenoxides are stoichiometric oxidants. Selenenamides, such as 2‐phenyl‐1,2‐benzisoselenazol‐3(2H)‐one (ebselen) and its analogues, known as glutathione peroxidase mimics acting via active hydroperoxide intermediates, are efficient and selective oxidation catalysts. Selenium(IV) oxide and some organoselenium compounds have been successfully applied for various oxidations useful in practical organic syntheses such as epoxidation, 1,2‐dihydroxylation, and α‐oxyfunctionalization of alkenes as well as for ring contraction of cycloalkanones, conversion of halomethyl, hydroxymethyl, or active methylene groups into formyl groups, oxidation of aldehydes into carboxylic acids, sulfides into sulfoxides, and secondary amines into nitrones, regeneration of parent carbonyl compounds from their azomethine derivatives and for other reactions. The oxidation mechanisms depend on the substrate and oxidant or catalyst used. The electrophilic center localized on the selenium atom or the nucleophilic center localized on the oxygen atom of the selenahydroperoxide group are involved in the reaction mechanism. In both cases the selenium‐containing moiety is a good leaving group. Exceptionally oxidation can proceed via free radical selenium species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

show abstract