- Extended and functionalized porous iron(iii) tri- or dicarboxylates with MIL-100/101 topologies
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A series of nanometric isoreticular and/or functionalized analogues of the mesoporous environmentally-friendly iron(iii) polycarboxylates MIL-100/101 have been successfully synthesized. Their exceptional pore size, of up to 68 ?, together with their relatively good stability in solvents, makes them promising candidates for heterogeneous catalysis or inclusion of large molecules, among others. the Partner Organisations 2014.
- Horcajada, Patricia,Chevreau, Hubert,Heurtaux, Daniela,Benyettou, Farah,Salles, Fabrice,Devic, Thomas,Garcia-Marquez, Alfonso,Yu, Cihang,Lavrard, Hubert,Dutson, Claire L.,Magnier, Emmanuel,Maurin, Guillaume,Elka?m, Erik,Serre, Christian
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supporting information
p. 6872 - 6874
(2014/06/23)
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- Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: Scope, limitations, and mechanistic features
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Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the ligandless CuCF3 at 23-50 C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While SNAr and SRN1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.
- Lishchynskyi, Anton,Novikov, Maxim A.,Martin, Eddy,Escudero-Adan, Eduardo C.,Novak, Petr,Grushin, Vladimir V.
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p. 11126 - 11146
(2013/12/04)
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- SYNTHESIS OF TEREPHTHALIC ACIDS CONTAINING POLYFLUOROALKYL GROUPS
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The syntheses of new terephthalic acids (8a-d) containing various polyfluoroalkyl groups (a ; CF3, b ; HCF2, c ; H(CF2)3 and d ; H(CF2)5) are described in this paper.These compounds were obtained by aromatization (bromination and dehydrobromination) of Di
- Kuwabara, Masaki,Murakami, Akira,Fukunishi, Koushi,Nomura, Mototeru,Yamanaka, Hiroki
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p. 105 - 118
(2007/10/02)
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