368-48-9Relevant articles and documents
Direct cupration of fluoroform
Zanardi, Alessandro,Novikov, Maxim A.,Martin, Eddy,Benet-Buchholz, Jordi,Grushin, Vladimir V.
, p. 20901 - 20913 (2011)
We have found the first reaction of direct cupration of fluoroform, the most attractive CF3 source for the introduction of the trifluoromethyl group into organic molecules. Treatment of CuX (X = Cl, Br, I) with 2 equiv of MOR (M = K, Na) in DMF or NMP produces novel alkoxycuprates that readily react with CF3H at room temperature and atmospheric pressure to give CuCF3 derivatives. The CuCl and t-BuOK (1:2) combination provides best results, furnishing the CuCF3 product within seconds in nearly quantitative yield. As demonstrated, neither CF3- nor CF2 mediate the Cu-CF3 bond formation, which accounts for its remarkably high selectivity. The fluoroform-derived CuCF3 solutions can be efficiently stabilized with TREAT HF to produce CuCF 3 reagents that readily trifluoromethylate organic and inorganic electrophiles in the absence of additional ligands such as phenanthroline. A series of novel Cu(I) complexes have been structurally characterized, including K(DMF)[Cu(OBu-t)2] (1), Na(DMF)2[Cu(OBu-t)2] (2), [K8Cu6(OBu-t)12(DMF)8(I)] + I- (3), and [Cu4(CF3) 2(C(OBu-t)2)2(μ3-OBu-t) 2] (7).
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Jarvie et al.
, p. 978 (1956)
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Discovery and characterization of a novel perylenephotoreductant for the activation of aryl halides
Guo, Baodang,Huang, Shuping,Li, Jia,Li, Min,Liu, Xuanzhong,Rao, Yijian,Wu, Yawen,Yin, Huimin,Yuan, Zhenbo,Zhang, Yan
, p. 111 - 120 (2021/06/16)
To develop a photocatalyst with catalytical activity for substrates with low reactivities is always highly desired. Herein, based on the principle of structure–property relationships, we rationally designed the natural product cercosporin, the naturally occurring perylenequinonoid pigment, to develop a novel organic perylenephotoreductant, hexacetyl reduced cercosporin (HARCP), through structural manipulation. Compared with cercosporin, HARCP shows prominent electrochemical and photophysical characteristics with greatly improved photoreductive activity, fluorescence lifetime and fluorescence quantum yield. These properties allowed HARCP as a powerful photoreductant to efficiently realize a series of benchmark reactions, including photoreduction, alkoxylation and hydroxylation to construct C–H and C–O bonds using aryl halides as substrates under mild conditions, all of which have never been achieved by the same photocatalyst. Thus, this study well supports the notion that the principle between structural manipulation and photocatalytic activity is of great significance to design customized photocatalysts for photoredox chemistry.
Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent
Akiyama, Takahiko,Ishikawa, Taisuke,Kamiyama, Nanami,Uchikura, Tatsuhiro
supporting information, p. 2442 - 2447 (2020/11/07)
The trifluoromethylation of iodoarenes was accomplished by use of a 2-trifluoromethylbenzimidazoline derivative as the trifluoromethylating reagent and a catalytic amount of Cu(I) in the presence of 2,2'-bipyridyl as the ligand. Through a mechanistic study, we found that the oxidative addition of the iodoarene to the Cu(I)–CF3 species is the rate-determining step.
Trifluoromethylation process for bromo-pyridine and derivatives thereof
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Paragraph 0060-0062, (2018/07/30)
The invention belongs to the field of organic chemistry and relates to a trifluoromethylation process for bromo-pyridine and derivatives thereof. The process disclosed by the invention comprises the following steps: by taking a bromo-pyridine compound with a formula a structure as a raw material, performing trifluoromethylation under the action of a Maben reagent fluoro-S-( trifluoromethyl)-dibenzothiophene salt having a formula c structure, thereby obtaining the tirfluoromethylpyridine compound with a formula b structure. The structural formula is as shown in the specification. In the formula, X- is Bronst conjugate base, R is H or -CN or halogen or C1-C6 alkyl or C1-C6 alkoxy or -OH or -R1OH or COR2 or -CO2R3 or -CONR4 or -NR5R6; R1 is C1-C6 akyl; R2, R3 and R4 are identically or differently H or C1-C6 alkyl; and the R5 and R6 are identically or differently H or O or C1-C6 alkyl or C1-C6 alkoxy.
