145299-89-4Relevant academic research and scientific papers
Light-mediated copper-catalyzed phosphorus/halogen exchange in 1,1-difluoroalkylphosphonium salts
Panferova, Liubov I.,Levin, Vitalij V.,Struchkova, Marina I.,Dilman, Alexander D.
, p. 1314 - 1317 (2019/01/30)
A method for the assembly of the halodifluoromethyl group (CF2X, X = Cl, Br, I) is described. The reaction involves the light-mediated substitution of the triphenylphosphine by halide anions in readily accessible gem-difluorinated phosphonium s
Stereoconvergent negishi arylations of racemic secondary alkyl electrophiles: Differentiating between a CF3 and an alkyl group
Liang, Yufan,Fu, Gregory C.
supporting information, p. 9523 - 9526 (2015/08/18)
In this report, we establish that a readily available nickel/bis(oxazoline) catalyst accomplishes a wide array of enantioconvergent cross-couplings of arylzinc reagents with CF3-substituted racemic secondary alkyl halides, a process that necessitates that the chiral catalyst be able to effectively distinguish between a CF3 and an alkyl group in order to provide good ee. We further demonstrate that this method can be applied without modification to the catalytic asymmetric synthesis of other families of fluorinated organic compounds.
Preparation of and fluoroalkylation with (chlorodifluoromethyl)trimethylsilane, difluorobis(trimethylsilyl)methane, and 1,1,2,2-tetrafluoro-1,2-bis(trimethylsilyl)ethane
Yudin, Andrei K.,Prakash, G. K. Surya,Deffieux, Denis,Bradley, Michael,Bau, Robert,Olah, George A.
, p. 1572 - 1581 (2007/10/03)
CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me3SiCF2Cl in high yield. Similarly, CF2Br2 gives Me3SiCF2Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me3SiCF2Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me3SiCF2Cl in the presence of chlorotrimethylsilane gives Me3SiCF2SiMe3 (anion-derived product) and Me3SiCF2CF2SiMe3 (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me3SiCF2SiMe3 difluoromethylates aldehydes acting as a difluoromethylene dianion ('CF22-'/equivalent), whereas Me3SiCF2CF2SiMe3 acts at room temperature as an in situ source for the perfluorovinyl anion (due to β-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion ('-CF2CF2-'/equivalent) behavior is observed. The structure of Me3SiCF2CF2SiMe3 was analyzed by X-ray diffraction. All of the studied fluoroalkylating reagents are moisture- and air-stable and can be readily obtained from a single convenient precursor (CF2BrCl).
Lewis Acid Catalyzed Aldol-Type Reaction of 1,1-Difluorovinyl Methyl Ether Derivatives
Kodama, Yoshitoshi,Yamane, Hidefumi,Okumura, Masato,Shiro, Motoo,Taguchi, Takeo
, p. 12217 - 12228 (2007/10/02)
In the presence of Lewis acid, such as SbCl5, SbCl6*NAr3 or Cu(OTf)2, difluorovinyl methyl ether (1,1-difluoro-2-methoxy-1-alkene) 1 reacted with carbonyl compounds to give O-methylated aldol-type products 3 in good yields, while Lewis acid, such as TMSOT
A microbially-based approach for the synthesis of chiral secondary alcohols bearing the difluoromethyl or chlorodifluoromethyl group
Kitazume, Tomoya,Asai, Masatomo,Tsukamoto, Takashi,Yamazaki, Takashi
, p. 271 - 284 (2007/10/02)
A synthetic approach to both enantiomers of the secondary alcohols , involving the stereoselective hydrolysis of ester derivatives, is described.The absolute configurations of these difluoromethylated or chlorodifluoromethylated molecules were determined.
