72993-29-4Relevant academic research and scientific papers
SYNTHESIS WITH MANGANIC SALTS; PART III: SYNTHESIS OF 1,4-DIKETONES THROUGH MANGANIC ACETATE-MEDIATED ADDITION OF KETONE TO ISOPENTENYL SULFONES. ACETOXYLATION OF Β,Γ-UNSATURATED KETONES BY MANGANOUS AND CUPRIC ACETATES
Breuilles, Pascal,Uguen, Daniel
, p. 705 - 720 (2007/10/02)
Conditions have been found to selectively add ketones to isopentenyl sulfones.The major product, a ketone bearing a methylene group at the γ position, gave upon ozonolysis the corresponding 1,4-diketone.The usefulness of the overall process was illustrated by the efficient syntheses of jasmone and of one half of pyrenophorine.The γ-acetoxy conjugated enones that invariably formed during these additions resulted from the oxidation of an isomeric β,γ-unsaturated ketone by manganous and cupric acetates.Such an acetoxylation has been used to prepare 6β-acetoxy-cholestenone from cholesterol and also to prepare chrysanthemic acid.
POLAR EFFECTS IN FREE-RADICAL REACTIONS. HOMOLYTIC ALKYLATION OF HETEROAROMATIC BASES BY Mn(III) OXIDATION OF ACETONE IN THE PRESENCE OF ALKENES
Citterio, Attilio,Gentile, Anna,Minisci, Francesco,Serravalle, Marco
, p. 443 - 448 (2007/10/02)
The oxidation of acetone in acetic acid by Mn(OAc)3 in the presence of olefins and heteroaromatic bases affords substitution products of the bases which can be explained by the addition of the electrophilic acetonyl radical to the olefinic double bond and scavenging of the resulting nucleophilic radical adduct by the bases.The addition reaction competes favourably with the oxidation of the alkyl radical adduct by Mn(OAc)3 only in the presence of a strong acid.The different polar character of the carbon-centred free radicals involved (acetonyl and alkyl) is responsible for the observed selective sequence which gives synthetic interest to the reaction.
