Lakk-Bogath, Dora; Kripli, Balazs; Meena, Bashdar I.; Speier, Gabor; Kaizer, Jozsef published the artcile< Catalytic and stoichiometric C-H oxidation of benzylalcohols and hydrocarbons mediated by nonheme oxoiron(IV) complex with chiral tetrapyridyl ligand>, Formula: C19H16O, the main research area is oxidation hydroxylation benzylalc hydrocarbon kinetic nonheme oxoiron complex.
Bioinspired chiral iron(II) complex [((R)-(-)-N4Py*)FeII(MeCN)]2+ (1) (N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) has been shown to efficiently catalyze the benzylic C-H oxidation of ethylbenzene with tert-Bu hydroperoxide (TBHP), H2O2, and meta-chloroperoxybenzoic acid (mCPBA) resulting in enantiomerically enriched 1-phenylethanol up to 12.5% ee and the corresponding acetophenone, where the [FeIV(N4Py*)(O)]2+ (2) intermediate has been detected by UV/visible spectrometry. The stoichiometric oxidation of benzyl alc. and various hydrocarbon derivatives including the asym. hydroxylation of ethylbenzene with 2 has also been investigated. Detailed kinetic, and mechanistic studies (kinetic isotope effect (KIE) of 31 and 38, and Hammett correlation with ρ = -0.32 and -0.98 for PhCH2OH and PhCH3, resp., and the linear correlation between the normalized bimol. reaction rates and bond dissociation energies (BDECH)) indicated that the rate-determining step in these reactions above involves hydrogen-atom transfer between the substrate and the Fe(IV)-oxo species. The stoichiometric 2-mediated hydroxylation of ethylbenzene affords 1-phenylethanol in up to 33% ee, suggesting clear evidence for the involvement of the oxoiron(IV) species in the enantioselective step. The moderate enantioselectivity may be explained by the epimerization of the long-lived substrate radical before the rebound step (non-rebound mechanism, where kep > kreb). The kinetic resolution of the resulting chiral alc. due to its metal-based overoxidn. process into acetophenone in the catalytic metal-based ethylbenzene oxidation can be excluded.
Inorganic Chemistry Communications published new progress about Aralkyl alcohols Role: RCT (Reactant), RACT (Reactant or Reagent) (benzylalcs.). 76-84-6 belongs to class alcohols-buliding-blocks, and the molecular formula is C19H16O, Formula: C19H16O.
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts