599-67-7Relevant articles and documents
Hydroxide-promoted Reduction of the Corrole Complexes of Cobalt(III) and Iron(III) in the Presence of Olefin
Murakami, Yukito,Aoyama, Yasuhiro,Hayashida, Mikio
, p. 501 - 502 (1980)
An oxygenation system effective for electronrich olefins which involves the hydroxide ion, provides electrons required for reduction of the corrole complexes of cobalt(III) and iron(III).
Photochemical polar addition of 1,1-diphenylethene using photosensitive surfactant in stable oil-in-water emulsion
Yoshimi, Yasuharu,Higuchi, Michiya,Itou, Tatsuya,Hatanaka, Minoru
, p. 1196 - 1197 (2004)
An aq NaOH solution of the photosensitive surfactant 1 was mixed with 1,1-diphenylethene 2 to form a stable oil-in-water emulsion and excitation of the emulsion afforded the alcohol 3 in good yield without stirring. The photosensitive surfactant 1 works more efficiently in heterogeneous system (in water) than in homogeneous system (in organic solvent).
PREPARATION AND REACTIONS OF SOLVENT-FREE ARYLCALCIUM HALIDES, ArCaX (X = F, Cl, Br)
Mochida, K.,Ogawa, H.
, p. 131 - 136 (1983)
Reactions of aryl halide vapor and calcium metal vapor were found to give the corresponding arylcalcium halides, ArCaX (X = F, Cl, and Br).Phenylcalcium halide, PhCaX (X = F and Cl), reacted with trimethylchlorosilane to give phenyltrimethylsilane.The reactions of phenylcalcium halides with acetone and benzaldehyde readily gave good yields of 1-methyl-1-phenylethanol and diphenylmethanol, respectively.Phenylcalcium halides reacted slowly with acetonitrile to afford acetophenone in poor yields.With ethyl acetate, phenylcalcium halides gave a mixture of 1,1-diphenylethanol and acetophenone.
Kinetic Isotope Effect and Substituent Effect Study on the Grignard Reaction of MeMgI with Benzophenone. A Rate-Determining C-C Bond Formation
Yamataka, Hiroshi,Matsuyama, Toyoki,Hanafusa, Terukiyo
, p. 647 - 650 (1987)
The carbonyl carbon-14 kinetic isotope effect and substituent effects were determined for the reaction of MeMgI with benzophenone.The observed large carbon isotope effect (14k/12k=1.056) together with the large steric effect on reactivity introduced by o-substituents on benzophenone indicated that the C-C bond formation is the rate-determinig step of the Grignard reaction.
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 (2021/05/31)
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.
A one-pot two-step synthesis of tertiary alcohols combining the biocatalytic laccase/TEMPO oxidation system with organolithium reagents in aerobic aqueous media at room temperature
Capriati, Vito,Cicco, Luciana,García-álvarez, Joaquín,González-Sabín, Javier,Lecuna, Ramón,Presa Soto, Alejandro,Ríos-Lombardía, Nicolás,Ramos-Martín, Marina,Vitale, Paola
, p. 13534 - 13537 (2021/12/23)
The one-pot/two-step combination of enzymes and polar organometallic chemistry in aqueous media is for the first time presented as a proof-of-concept study. The unprecedented combination of the catalytic oxidation of secondary alcohols by the system laccase/TEMPO with the ultrafast addition (3 s reaction time) of polar organometallic reagents (RLi/RMgX) to thein situformed ketones, run under air at room temperature, allows the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions (up to 96%).
Expeditious and practical synthesis of tertiary alcohols from esters enabled by highly polarized organometallic compounds under aerobic conditions in Deep Eutectic Solvents or bulk water
Quivelli, Andrea F.,D'Addato, Giovanna,Vitale, Paola,García-álvarez, Joaquín,Perna, Filippo M.,Capriati, Vito
, (2021/01/18)
An efficient protocol was developed for the synthesis of tertiary alcohols via nucleophilic addition of organometallic compounds of s-block elements (Grignard and organolithium reagents) to esters performed in the biodegradable choline chloride/urea eutectic mixture or in water. This approach displays a broad substrate scope, with the addition reaction proceeding quickly (20 s reaction time) and cleanly, at ambient temperature and under air, straightforwardly furnishing the expected tertiary alcohols in yields of up to 98%. The practicability of the method is exemplified by the sustainable synthesis of some representative S-trityl-L-cysteine derivatives, which are a potent class of Eg5 inhibitors, also via telescoped one-pot processes.
