357274-85-2Relevant articles and documents
4-Difluoromethylated quinoline synthesis via intramolecular S N2′ reaction of α-trifluoromethylstyrenes bearing imine moieties
Mori, Takashi,Ichikawa, Junji
, p. 1206 - 1207 (2004)
Intramolecular cyclization of o-methyleneamino-substituted α-trifluoromethylstyrenes is promoted by DBU and a catalytic amount of KCN to provide 4-(difluoromethyl)quinolines. The reaction proceeds via (i) the generation of carbon nucleophiles from the imi
Suzuki coupling of aroyl-MIDA boronate esters – A preliminary report on scope and limitations
Lai, Samson,Lin, Wen Xuan,Perrin, David M.,Takaesu, Noah
supporting information, (2021/05/31)
Recent methodological reports for synthesizing acyl-MIDA boronate esters compel an investigation of their potential use as substrates in a standard Suzuki-Miyaura cross-coupling reaction. Here we report the production of benzophenones by C[sbnd]C cross coupling between a benzoyl-MIDA boronate ester and a multitude of aryl bromide substrates in adequate yields following optimization under ambient conditions outside of a glove box. Under these standard conditions, none of several acyl-MIDA boronate esters (in an alkyl series) serves as a competent coupling partner. The substrate scope is also limited by the finding that the corresponding trifluoroborates of both acyl- and aroyltrifluroborates are not suitable substrates. For reasons of availability and synthetic difficulty in procuring other aroyl-MIDA boronates, this preliminary study examines the reactivity of benzoyl-MIDA boronate with several aryl bromide substrates.
Catalytic Enantioselective Synthesis of Heterocyclic Vicinal Fluoroamines by Using Asymmetric Protonation: Method Development and Mechanistic Study
Ashford, Matthew W.,Xu, Chao,Molloy, John J.,Carpenter-Warren, Cameron,Slawin, Alexandra M. Z.,Leach, Andrew G.,Watson, Allan J. B.
supporting information, p. 12249 - 12255 (2020/08/21)
A catalytic enantioselective synthesis of heterocyclic vicinal fluoroamines is reported. A chiral Br?nsted acid promotes aza-Michael addition to fluoroalkenyl heterocycles to give a prochiral enamine intermediate that undergoes asymmetric protonation upon rearomatization. The reaction accommodates a range of azaheterocycles and nucleophiles, generating the C?F stereocentre in high enantioselectivity, and is also amenable to stereogenic C?CF3 bonds. Extensive DFT calculations provided evidence for stereocontrolled proton transfer from catalyst to substrate as the rate-determining step, and showed the importance of steric interactions from the catalyst's alkyl groups in enforcing the high enantioselectivity. Crystal structure data show the dominance of noncovalent interactions in the core structure conformation, enabling modulation of the conformational landscape. Ramachandran-type analysis of conformer distribution and Protein Data Bank mining indicated that benzylic fluorination by this approach has the potential to improve the potency of several marketed drugs.
Flash generation and borylation of 1-(trifluoromethyl)vinyllithium toward synthesis of α-(trifluoromethyl)styrenes
Fujita, Takeshi,Konno, Naruki,Watabe, Yota,Ichitsuka, Tomohiro,Nagaki, Aiichiro,Yoshida, Jun-ichi,Ichikawa, Junji
, p. 72 - 76 (2018/02/09)
Thermally unstable (3,3,3-trifluoroprop-1-en-2-yl)lithium was generated by lithiation of 2-bromo-3,3,3-trifluoroprop-1-ene and successively underwent borylation in a flow microreactor system. Direct use of the 1-(trifluoromethyl)vinylborate thus formed for the Suzuki–Miyaura coupling in a batch system afforded α-(trifluoromethyl)styrenes in high yields.
Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics
Lang, Simon B.,Wiles, Rebecca J.,Kelly, Christopher B.,Molander, Gary A.
supporting information, p. 15073 - 15077 (2017/11/20)
Described is a facile, scalable route to access functional-group-rich gem-difluoroalkenes. Using visible-light-activated catalysts in conjunction with an arsenal of carbon-radical precursors, an array of trifluoromethyl-substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two-electron pathways. The process readily extends to other perfluoroalkyl-substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl-substituted alkene starting materials.
Synthesis of isochromanes and isothiochromanes bearing fluorinated one-carbon units via intramolecular cyclizations of ortho-substituted α-(trifluoromethyl)styrenes
Ichikawa, Junji,Ikeda, Masahiro,Hattori, Masahiro
experimental part, p. 1285 - 1296 (2010/10/19)
α-(Trifluoromethyl)styrenes bearing a nucleophilic oxygen or sulfur atom tethered by a methylene or methyne unit at the ortho carbon were prepared by the coupling reaction of 2-bromo-3,3,3-trifluoropropene with aryl iodides via (3,3,3-trifluoroprop-l-en-2
Substituted arylpyrazoles
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Page/Page column 27, (2008/06/13)
This invention relates to a range of 1-aryl-4-cyclopropylpyrazoles in which there is at least one fluorine attached to the cyclopropyl ring, to compositions comprising such compounds, processes to their synthesis and their use as parasiticides.
α-(Trifluoromethyl)ethenyl boronic acid as a useful trifluoromethyl containing building block. Preparation and palladium-catalysed coupling with aryl halides
Jiang, Biao,Wang, Quan-Fu,Yang, Cai-Guang,Xu, Min
, p. 4083 - 4085 (2007/10/03)
α-(Trifluoromethyl)ethenyl boronic acid was conveniently prepared from the reaction of readily available 2-bromotrifluoropropene with alkyl borate and magnesium in one-pot. This boronic acid can undergo palladium-catalysed coupling reactions with aryl halides to afford a series of useful α-(trifluoromethyl)styrene derivatives in high yield.
