- Fluoroform: an Efficient Precursor for the Trifluoromethylation of Aromatic Esters by Sodium Diisopropylamide with Trialkylamines
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The trifluoromethanide anion is the postulated key intermediate in nucleophilic trifluoromethylation reactions. It is believed to be incompatible with Na+ cation due to the strong Na–F bond. However, herein we demonstrate that it could be prepared for the first time. Trialkylamines can be used as cation chelating agents to stabilize the isolated –CF3 ion to realize trifluoromethylation reaction. With this strategy, trifluoromethyl aromatic ketones could be effectively synthesized from fluoroform and aromatic esters with diisopropyl aminosodium (NaDA) and trialkylamines.
- Han, Zhaomeng,Chen, Sihan,Tu, Yongjun,Lian, Xiongdong,Li, Gongyong
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supporting information
p. 4658 - 4661
(2019/08/07)
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- Enantioselective Synthesis of Trifluoromethyl α,β-Unsaturated δ-Lactones via Vinylogous Aldol-Lactonization Cascade
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The novel vinylogous aldol-lactonization cascade of alkylidene oxindole with trifluoromethyl ketones is presented. The reaction, catalyzed by a bifunctional tertiary amine, provides an efficient application of the vinylogous reactivity of alkylidene oxindoles for the preparation of enantioenriched trifluoromethylated α,β-unsaturated δ-lactones.
- Crotti, Simone,Di Iorio, Nicola,Mazzanti, Andrea,Righi, Paolo,Bencivenni, Giorgio
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p. 12440 - 12448
(2018/10/09)
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- Visible light-promoted umpolung coupling of aryl tri-/difluoroethanones with 2-alkenylpyridines
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Tertiary alcohols bearing a trifluoromethyl group are of considerable medicinal interest. Using an umpolung strategy, we herein report the first intermolecular reductive cross-coupling of aryl tri-/difluoroethanones with 2-alkenylpyridines with the aid of a Br?nsted acid catalyst upon visible-light irradiation. This metal-free reaction is operationally simple and performed at ambient temperature, allowing access to desired tertiary alcohols with tri-/difluoromethyl groups in moderate to excellent yields. The commercially available and easily handled Hantzsch ester effectively serves as an electron donor, as well as a hydrogen atom source.
- Xu, Xiao,Min, Qing-Qiang,Li, Na,Liu, Feng
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p. 11017 - 11020
(2018/10/08)
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- High-Pressure-Mediated Asymmetric Organocatalytic Hydroxyalkylation of Indoles with Trifluoromethyl Ketones
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An enantioselective hydroxyalkylation of indoles and 7-azaindole with trifluoromethyl ketones was found to be effectively promoted under high-pressure conditions with a low loading of Cinchona alkaloids (e.g., 1–3 mol% of cinchonidine). Chiral tertiary alcohols containing a trifluoromethyl group were obtained at 9 kbar with good yield and enantioselectivity up to 89%, whereas usually merely traces of products were detected at atmospheric pressure. (Figure presented.).
- Kasztelan, Adrian,Biedrzycki, Micha?,Kwiatkowski, Piotr
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supporting information
p. 2962 - 2969
(2016/09/16)
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- Synthesis of 3-fluoromethyl-2,1-benzisoxazoles
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A convenient synthetic method to access hitherto unknown 3-(trifluoromethyl)- and 3-(difluoromethyl)-2,1-benzisoxazoles by the reaction of sodium azide with 1-(2-halophenyl)-2,2,2-trifluoroethanones or 1-(2-halophenyl)-2,2-difluoroethanones was developed. 3-Fluoromethyl-2,1-benzisoxazoles are versatile precursors for o-fluoroacetylanilines.
- Golubev,Shidlovskii,Peregudov,Kagramanov
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p. 2264 - 2270
(2015/06/22)
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- Highly efficient synthesis of aryl and heteroaryl trifluoromethyl ketones via o-iodobenzoic acid (IBX)
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A two-step process for the synthesis of aryl and heteroaryl trifluoromethyl ketones from the corresponding aldehydes is described. Trifluoromethyl alcohols were prepared from aryl and heteroaryl aldehydes in excellent yields using catalytic amount of K2CO3. The trifluoromethyl alcohols were then oxidized conveniently and efficiently by o-iodoxybenzoic acid (IBX) under mild conditions to get the desired functionalized aryl and heteroaryl trifluoromethyl ketones.
- Cheng, Huicheng,Pei, Yu,Leng, Faqiang,Li, Jingya,Liang, Apeng,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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p. 4483 - 4486
(2013/07/26)
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- A new entry for the oxidation of fluoroalkyl-substituted methanol derivatives: Scope and limitation of the organoiodine(V) reagent-catalyzed oxidation
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Oxidation of various fluoroalkyl-substituted methanol derivatives under the influence of a catalytic amount of sodium 2-iodobenzenesulfonate and Oxone in CH3CN or CH3NO2 was investigated in detail. The efficiency of the newly developed oxidation was also evaluated by comparison to other oxidations, such as Dess-Martin, PDC, and Swern oxidation.
- Tanaka, Yusuke,Ishihara, Takashi,Konno, Tsutomu
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experimental part
p. 99 - 104
(2012/05/07)
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