383-63-1Relevant articles and documents
Stable carbocations XXIII. Generation and isolation of salts of ferrocenyl(alkoxy)methylium cations and their intermediacy in acid-promoted acetal hydrolysis
Kenny, T. P. E.,Knipe, A. C.,Watts, W. E.
, p. 257 - 261 (1991)
Ferrocenyl(aloxy)methylium cations have been generated from (dialkoxymethyl)ferrocenes and isolated as tetrafluoroborate salts.Their structures and their reactivity towards nucleophiles have been investigated.
Barnes et al.
, p. 2175,2176-2178 (1972)
A facial chemoenzymatic method for the preparation of chiral 1,2-dihydroxy-3,3,3,-trifluoropropanephosphonates
Yuan, Chengye,Li, Jinfeng,Zhang, Wenchi
, p. 44 - 47 (2006)
A convenient and effective method for the preparation of chiral trifluoromethylated 1,2-dihydroxypropanephosphonates based on a chemoenzymatic approach was described. Ethyl trifluoromethylacetate was reacted with anion of methylphosphonate to give 2-oxo-3,3,3-trifluoropropanephosphonate and its hydrates, 2,2-dihydroxy-3,3,3-trifluoropropanephosphonates, which are reduced with sodium boronhydride affording 2-hydroxy-3,3,3-trifluoropropanephosphonates. The product thus obtained was then transferred to corresponding 1,2-vinyl-3,3,3-trifluoropropanephosphonate and followed by 1,2-dihydroxylation via potassium permanganate treatment. Enzymatic kinetic resolution of the resultant racemate by CALB or IM provided optically active 1,2-dihydroxy-3,3,3- trifluoropropanephosphonate with satisfactory chemical and enantiomeric yield.
Electrocatalytic Oxyesterification of Hydrocarbons by Tetravalent Lead
Haviv, Eynat,Herman, Adi,Khenkin, Alexander M.,Neumann, Ronny
, p. 10494 - 10501 (2021/08/31)
The selective catalytic oxidative monofunctionalization of gaseous alkanes found in natural gas and commodity chemicals such as benzene and cyclohexane is an important objective in the field of carbon-hydrogen bond activation. Past research has demonstrated the possibility of stoichiometric oxyesterification of such substrates using lead(IV) trifluoroacetate (PbIV(TFA)4) as oxidant, which is driven by the high 2-electron redox potential of lead(IV). However, this redox potential then precludes reoxidation of lead(II) by a convenient oxidant such as O2, nullifying an effective catalytic cycle. In order to utilize renewable energy resources as alternatives to high-temperature thermocatalysis, we demonstrate the room-temperature electrocatalytic oxyesterification of alkanes and benzene with PbIV(TFA)4 as catalysts. At 1.67 V versus SHE, alkanes and benzene yielded the corresponding trifluoroacetate esters at room temperature; typically, good yields and high faradaic efficiencies were observed. High intrinsic turnover frequencies were obtained, for example, of >1000 min-1 for the oxyesterification of ethane at 30 bar. An analysis of the possible mechanistic pathways based on previously investigated stochiometric reactions, cyclic voltammetry measurements, kinetic isotope effects, and model compounds led to the conclusion that catalysis involves lead-mediated proton-coupled electron transfer of alkanes at and to the anode, followed by reductive elimination through an SN2 reaction to yield the alkyl-TFA products. Similarly, lead-mediated electron transfer from benzene at and to the anode leads to phenyl-TFA. Cyclic voltammetry also shows the viability of in situ reoxidation of Pb(II) species. The synthesis results obtained as well as the mechanistic insight are important advances towards the realization of selective alkane and arene oxidation reactions.
Oxidation of fluoroalkyl alcohols using sodium hypochlorite pentahydrate [1]
Kirihara, Masayuki,Suzuki, Katsuya,Nakakura, Kana,Saito, Katsuya,Nakamura, Riho,Tujimoto, Kazuki,Sakamoto, Yugo,Kikkawa, You,Shimazu, Hideo,Kimura, Yoshikazu
, (2021/02/05)
Fluoroalkyl alcohols are effectivity oxidized to the corresponding fluoroalkyl carbonyl compounds by reaction with sodium hypochlorite pentahydrate in acetonitrile in the presence of acid and nitroxyl radical catalysts. Although the reaction proceeded slower under a nitroxyl radical catalyst- free condition, the desired carbonyl compounds were obtained in high yields. For the reaction with fluoroalkyl allylic alcohols, the corresponding α,β-epoxyketone hydrates were obtained in high yields.