10541-59-0Relevant articles and documents
Preparation of 1,1-difluoroalkanes from aldehydes via 1,1-bistriflates: Advantageous use of HF-Lewis base reagents
Dolbier, William R.,Okamoto, Masamune
, p. 96 - 100 (2014)
Alkane-1,1-bistriflates, prepared in excellent yields by reaction of aldehydes with triflic anhydride, are converted to their respective 1,1-difluoroalkanes in good to excellent yield through reaction with fluorinating agent, triethylaminetrishydrofluorid
Zupan,Pollak
, p. 715 (1975)
Hypervalent Iodine-Mediated Fluorination of Styrene Derivatives: Stoichiometric and Catalytic Transformation to 2,2-Difluoroethylarenes
Kitamura, Tsugio,Muta, Kensuke,Oyamada, Juzo
, p. 10431 - 10436 (2015)
Fluorination of styrene derivatives with a reagent system composed of μ-oxo-bis[trifluoroacetato(phenyl)iodine] and a pyridine·HF complex gave the corresponding (2,2-difluoroethyl)arenes in good yields. Similarly, the reagent of PhI(OCOCF3)2 and the pyridine·HF complex acted as a fluorinating agent for styrene derivatives. The fluorination of styrene derivatives with the pyridine·HF complex underwent under catalytic conditions using 4-iodotoluene as a catalyst and m-CPBA as a terminal oxidant.
Mild silver-mediated geminal difluorination of styrenes using an air- and moisture-stable fluoroiodane reagent
Ilchenko, Nadia O.,Tasch, Boris O. A.,Szabó, Kálmán J.
, p. 12897 - 12901 (2014)
An air- and moisture-stable fluoroiodane in the presence of AgBF4 is suitable for selective geminal difluorination of styrenes under mild reaction conditions. One of the C-F bonds is formed by transfer of electrophilic fluorine from the hypervalent iodine reagent, while the other one arises from the tetrafluoroborate counterion of silver. Deuterium-isotope-labelling experiments and rearrangement of methyl styrene substrates suggest that the reaction proceeds through a phenonium ion intermediate. Phenomenal phenonium: A formal F2 addition to styrenes was carried out by using stable and safe fluorinating reagents under mild reaction conditions. The reaction proceeds via a phenonium intermediate.
Aryl Radical Activation of C-O Bonds: Copper-Catalyzed Deoxygenative Difluoromethylation of Alcohols
Cai, Aijie,Liu, Wei,Yan, Wenhao
, p. 9952 - 9960 (2021/07/21)
Given their ubiquity in natural products and pharmaceuticals, alcohols represent one of the most attractive starting materials for the construction of C-C bonds. We report herein the first catalytic strategy to harness the reactivity of aryl radicals for the activation of C-O bonds in alcohol-derived xanthate esters, allowing for the discovery of the first catalytic deoxygenative difluoromethylation reaction. Under copper-catalyzed conditions, a wide variety of alkyl xanthate esters, readily synthesized from alcohol feedstocks, were activated by catalytically generated aryl radicals and were converted to the alkyl-difluoromethane products via alkyl radical intermediates. This scalable protocol exhibits a broad substrate scope and functional group tolerance, enabling late-stage modification of complex pharmaceutical agents. A one-pot protocol has been developed that allows for the direct use of free alcohols without purification of the xanthate esters. Mechanistic studies are consistent with the hypothesis of aryl radicals being formed and initiating the cleavage of the C-O bonds of xanthate esters, to generate alkyl radicals as the key intermediates. This aryl radical activation approach represents a new strategy for the activation of alcohols as cross-coupling partners.
Reactions of organozinc reagents with potassium bromodifluoroacetate
Levin, Vitalij V.,Zemtsov, Artem A.,Struchkova, Marina I.,Dilman, Alexander D.
, p. 97 - 101 (2015/03/04)
A practical method for the synthesis of gem-difluorinated compounds from organozinc reagents is described. Potassium bromodifluoroacetate serves as a source of CF2-fragment, which is inserted into carbonzinc bond of organozinc reagents. The intermediate difluorinated organozinc species can be protonated, brominated or coupled with allylic electrophiles.
