- Radical C?H Trifluoromethoxylation of (Hetero)arenes with Bis(trifluoromethyl)peroxide
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Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C?H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches.
- Dix, Stefan,Golz, Paul,Schmid, Jonas R.,Riedel, Sebastian,Hopkinson, Matthew N.
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supporting information
p. 11554 - 11558
(2021/07/09)
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- Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow
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The first example of photocatalytic trifluoromethoxylation of arenes and heteroarenes under continuous-flow conditions is described. Application of continuous-flow microreactor technology allowed to reduce the residence time up to 16 times in comparison t
- Cendón, Borja,Gulías, Moisés,Ho, Michelle,No?l, Timothy,Nyuchev, Alexander V.,Sambiagio, Carlo,Struijs, Job J. C.,Wan, Ting,Wang, Ying
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supporting information
p. 1305 - 1312
(2020/07/10)
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- Sequential Xanthalation and O-Trifluoromethylation of Phenols: A Procedure for the Synthesis of Aryl Trifluoromethyl Ethers
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Molecules containing trifluoromethoxyaryl groups are of interest in pharmaceutical, agrochemical, and materials science research, due to their unique physical and electronic properties. Many of the known methods to synthesize aryl trifluoromethyl ethers require harsh reagents and highly controlled reaction conditions and rarely occur when heteroaromatic units are present. The two-step O-trifluoromethylation of phenols via aryl xanthates is one such method that suffers from these drawbacks. Herein, we report a method for the synthesis of aryl trifluoromethyl ethers from phenols by the facile conversion of the phenol to the corresponding aryl and heteroaryl xanthates with newly synthesized imidazolium methylthiocarbonothioyl salts and conversion of these xanthates to the trifluoromethyl ethers under mild reaction conditions.
- Yoritate, Makoto,Londregan, Allyn T.,Lian, Yajing,Hartwig, John F.
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p. 15767 - 15776
(2019/12/04)
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- Visible-Light Photoredox-Catalyzed and Copper-Promoted Trifluoromethoxylation of Arenediazonium Tetrafluoroborates
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We report the development of photoredox-catalyzed and copper-promoted trifluoromethoxylation of arenediazonium tetrafluoroborates, with trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxylation reagent. This new method takes advantage of visible-light photoredox catalysis to generate the aryl radical under mild conditions, combined with copper-promoted selective trifluoromethoxylation. The reaction is scalable, tolerates a wide range of functional groups, and proceeds regioselectively under mild reaction conditions. Furthermore, mechanistic studies suggested that a Cs[Cu(OCF3)2] intermediate might be generated during the reaction.
- Yang, Shaoqiang,Chen, Miao,Tang, Pingping
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supporting information
p. 7840 - 7844
(2019/05/15)
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- Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N?O Bond Redox Fragmentation
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A simple trifluoromethoxylation method enables non-directed functionalization of C?H bonds on a range of substrates, providing access to aryl trifluoromethyl ethers. This light-driven process is distinctly different from conventional procedures and occurs through an OCF3 radical mechanism mediated by a photoredox catalyst, which triggers an N?O bond fragmentation. The pyridinium-based trifluoromethoxylation reagent is bench-stable and provides access to synthetic diversity in lead compounds in an operationally simple manner.
- Jelier, Benson J.,Tripet, Pascal F.,Pietrasiak, Ewa,Franzoni, Ivan,Jeschke, Gunnar,Togni, Antonio
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supporting information
p. 13784 - 13789
(2018/09/14)
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- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
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A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
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supporting information
p. 14622 - 14626
(2018/09/21)
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- Direct Pd(II)-Catalyzed Site-Selective C5-Arylation of 2-Pyridone Using Aryl Iodides
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A straightforward Pd(II)-catalyzed general strategy was developed for the C5-selective arylation of the 2-pyridone core with easily available aryl iodides. The transformation was highly regioselective and accomplished with a wide scope and functional group tolerance. Silver nitrate played a crucial role in this direct site-selective arylation. The method was extended to synthesize biologically active molecules.
- Maity, Saurabh,Das, Debapratim,Sarkar, Souradip,Samanta, Rajarshi
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supporting information
p. 5167 - 5171
(2018/09/13)
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- Synthesis and antiproliferative activity of novel 4-substituted-phenoxy-benzamide derivatives
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A series of novel 4-substituted-phenoxy-benzamide derivatives bearing an aryl cycloaliphatic amine moiety were synthesized and evaluated for antiproliferative activity against SW620, HT29 and MGC803 cancer cell lines in vitro. The pharmacological data demonstrated that the majority of target compounds exhibited moderate efficacy in HT29 and MGC803 cell lines. Compound 10c showed promising inhibition of hedgehog (Hh) signaling pathway in an Hh-related assay. In addition, the superposition pattern of 10c showed a good fit for a pharmacophoric model generated by Hh inhibitors and provided a basis for further structural optimization.
- Sun, Chi-Yu,Li, Yang-Sheng,Shi, Ai-Long,Li, Ya-Fei,Cao, Rui-Fang,Ding, Huai-Wei,Yin, Qing-Qing,Zhang, Li-Juan,Zheng, Hua-Chuan,Song, Hong-Rui
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supporting information
p. 1307 - 1310
(2015/12/31)
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- 2-, 3-, and 4-(Trifluoromethoxy)phenyllithiums: Versatile intermediates offering access to a variety of new organofluorine compounds
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Consecutive treatment of (trifluoromethoxy)benzene with sec-butyllithium and electrophilic reagents affords previously inaccessible ortho-substituted derivatives in generally excellent yields. 2-(Trifluoromethoxy)phenyllithium acts as the key intermediate. The 3- and 4-isomers can readily be generated from the corresponding 3- and 4-bromo precursors by halogen-metal interconversion with butyllithium or tertbutyllithium. Upon trapping of the 2-, 3- and 4-(trifluoromethoxy)phenyllithiums with 11 different electrophiles the expected products were formed in generally high yields. Only the attempted nucleophilic addition of 2-(trifluoromethoxy)phenyllithium to oxirane did not succeed. This failure is tentatively attributed to a lowering of the nucleophilicity by fluorine-lithium interactions. Conformationally restricted analogs - i.e., 2,2-difluoro-1,3-benzodioxol-4-phenyllithium and its 5-fluoro- and 5-bromo-substituted congeners - did indeed react smoothly with oxirane, affording the adducts in ordinary yields.
- Castagnetti, Eva,Schlosser, Manfred
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p. 691 - 695
(2007/10/03)
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- Antifugal azole compounds
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1,3-Diazolyl-2-propanol derivatives of the formula STR1 wherein X and Y are N or CH, R1 is phenyl, heterocyclyl, heterocyclyl-alkyl, -alkenyl or -alkynyl, optionally substituted, R2 and R3 are hydrogen or alkyl, and R4 and R5 are hydrogen, amino, alkoxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, or alkenyl, or phenyl, phenylalkyl or phenylalkenyl, heterocycyl, heterocyclyalkyl or heterocyclylalkenyl, each optionally substituted, provided that when R1 is optionally substituted phenyl at least one of R1, R4 and R5 is, or contains, a phenyl ring bearing at least one substitutent selected from cyano, cyanoalkyl, nitro, aminocarbonylalkyl, halogeneoalkoxy and radicals of the formulae --CONR6 R7, --NHCOR8 or OR9 as defined herein, and the acid addition salts of compounds which contain a basic substituent; together with processes for their manufacture, pharmaceutical, veterinary and plant antifungal compositions, a method of treating fungal diseases in plants, and the use of the compounds for the manufacture of pharmacuetical or veterinary antifungal compositions.
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