Etude par analyse enthalpique différentielle de la stabilité de peroxycetals

Helgorsky, Catherine; Bevilacqua, Marcel; Degueil-Castaing, Marie; Maillard, B.

doi:10.1016/s0040-6031(97)00155-x

Cited by 3 publications

(2 citation statements)

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“…The combination of a titanium(IV) alkoxide and a siloxane proved to be a useful terminal reductant for the phosphine-catalyzed reduction of protected hydroperoxides. , When benzyl peroxide 1c was treated with catalytic amounts of phosphine in the presence of titanium isopropoxide (Ti(O- i -Pr) 4 ) and HSiMe 2 OSiMe 2 H (1,1,3,3-tetramethyldisiloxane, TMDS), only alcohol 3 and unreacted starting material 1c were isolated from the reaction mixture (Table , entry 1). Ketal 1d underwent decomposition to an unknown product under the catalytic reducing conditions (Table , entry 2) . Reduction was much cleaner when a silyl protecting group was used for the peroxide (Table , entry 3).…”

Section: Resultsmentioning

confidence: 99%

Phosphine-Catalyzed Reductions of Alkyl Silyl Peroxides by Titanium Hydride Reducing Agents: Development of the Method and Mechanistic Investigations

et al. 2010

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A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with (17)O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

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Section: Resultsmentioning

confidence: 99%

Phosphine-Catalyzed Reductions of Alkyl Silyl Peroxides by Titanium Hydride Reducing Agents: Development of the Method and Mechanistic Investigations

et al. 2010

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“…Different peroxy acetals and peroxy ketals including and cyclic polyperoxides are formed in acidic media as a result of condensation of aldehydes or ketones with 1-hydroxyperoxides. 188,189 The thermolysis of monoperoxy ketals 190 is characterised by the parameters listed in Table 25. Despite the large distance between the peroxide group and the substituent, the structure of the latter has a strong effect on the kinetic parameters of the thermolysis.…”

Section: Peroxide Derivatives Of Carbonyl Compoundsmentioning

confidence: 99%