10042-36-1Relevant articles and documents
To Rebound or...Rebound? Evidence for the "alternative Rebound" mechanism in Ca'H Oxidations by the systems nonheme Mn Complex/H2O2/carboxylic acid
Ottenbacher, Roman V.,Bryliakova, Anna A.,Shashkov, Mikhail V.,Talsi, Evgenii P.,Bryliakov, Konstantin P.
, p. 5517 - 5524 (2021)
In this work, it has been shown that aliphatic Ca'H oxidations by bioinspired catalyst systems Mn aminopyridine complex/H2O2/carboxylic acid in acetonitrile afford predominantly a mixture of the corresponding alcohol and the ester. The alcohol/ester ratio is higher for catalysts bearing electron-donating groups at the aminopyridine core. Isotopic labeling studies witness that the oxygen atom of the alcohol originates from the H2O2molecule, 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-phenyl acetate, with close enantioselectivities and the same sign of absolute chirality. Experimental data and density 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 Ca'H oxidations catalyzed by bioinspired Mn complexes. The trends governing the alcohol/ester ratios have been rationalized in terms of steric properties of the catalyst, acid, and substrate. copy; 2021 American Chemical Society.
Development of more potent 4-dimethylaminopyridine analogues
Singh, Satwinder,Das, Goutam,Singh, Om V.,Han, Hyunsoo
, p. 401 - 404 (2007)
The syntheses of bicyclic diaminopyridines 3 and 4 and tricyclic triaminopyridines 5 and 6, two novel series of nucleophilic catalysts, are described. Arguments are made for predicting the superiority of these catalysts over DMAP and even 2, the best esterification catalyst reported to date. The efficiencies of DMAP, PPY, and 2-6 in catalyzing the esterification of tertiary alcohols were compared. As predicted, 5 and 6 were about 6-fold more effective than DMAP and slightly better than 2.
Iron-Catalyzed Acyloxyalkylation of Styrenes Using Hypervalent Iodine Reagents
Wang, Zijia,Kanai, Motomu,Kuninobu, Yoichiro
supporting information, p. 2398 - 2401 (2017/05/12)
Iron-catalyzed acyloxyalkylation of styrene derivatives using hypervalent iodine reagents was achieved. The acyloxyalkylation reaction proceeded using various types of styrenes and hypervalent iodine reagents. The acyloxyalkylated products were obtained in moderate to good yields without loss of the functional groups. The reaction proceeded via the formation of radical species derived from hypervalent iodine reagents by decarboxylation.