Ottenbacher, Roman V.; Bryliakova, Anna A.; Shashkov, Mikhail V.; Talsi, Evgenii P.; Bryliakov, Konstantin P. published the artcile< To Rebound or...Rebound? Evidence for the ""Alternative Rebound"" Mechanism in C-H Oxidations by the Systems Nonheme Mn Complex/H2O2/Carboxylic Acid>, Reference of 76-84-6, the main research area is oxidation mechanism nonheme manganese complex hydrogen peroxide carboxylic acid.
In this work, it has been shown that aliphatic C-H oxidations by bioinspired catalyst systems Mn aminopyridine complex/H2O2/carboxylic acid in acetonitrile afford predominantly a mixture of the corresponding alc. and the ester. The alc./ester ratio is higher for catalysts bearing electron-donating groups at the aminopyridine core. Isotopic labeling studies witness that the oxygen atom of the alc. originates from the H2O2 mol., while the ester oxygen comes exclusively from the acid. Oxidation of ethylbenzene in the presence of acetic acid affords enantiomerically enriched 1-phenylethanol and 1-Ph acetate, with close enantioselectivities and the same sign of absolute chirality. Exptl. data and d. functional theory calculations provide evidence in favor of the rate-limiting benzylic H atom abstraction by the high-spin (S = 1) [LMnV(O)OAc]2+ active species followed by competitive OH/OC(O)R rebound. This mechanism has been unprecedented for C-H oxidations catalyzed by bioinspired Mn complexes. The trends governing the alc./ester ratios have been rationalized in terms of steric properties of the catalyst, acid, and substrate.
ACS Catalysis published new progress about Alkylarenes Role: RCT (Reactant), RACT (Reactant or Reagent). 76-84-6 belongs to class alcohols-buliding-blocks, and the molecular formula is C19H16O, Reference of 76-84-6.
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts