Structure and conformation of α,α,α-trifluoroanisol, C 6 H 5 OCF 3

Federsel, Daniela; Herrmann, Angelika; Christen, Dines; Sander, Stefan; Willner, Helge; Oberhammer, Heinz

doi:10.1016/s0022-2860(01)00541-5

Cited by 71 publications

(56 citation statements)

References 24 publications

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“…1a), which prevents the free rotation of the adjacent amide or carbamate group (see ESI † ). 7,42–45 Finally, the regioselectivity erodes as the reaction temperature increases ( 2d – f , 2o , 2u ).…”

Section: Resultsmentioning

confidence: 99%

“…First of all, in aryl trifluoromethyl ethers the OCF 3 moiety lies in the plane orthogonal to arene ring (Fig. 1a) 7 and studies have shown that this unusual orientation may be beneficial for providing additional binding affinity in drug–target complexes. 8 In addition, the OCF 3 group is among the most electronegative groups ( χ ( F ) = 4.0, χ (OCF 3 ) = 3.7).…”

Section: Introductionmentioning

confidence: 99%

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Access to a new class of synthetic building blocks via trifluoromethoxylation of pyridines and pyrimidines

Feng

Lee

et al. 2016

Chem. Sci.

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Since the first synthesis of trifluoromethyl ethers in 1935, the trifluoromethoxy (OCF3) group has made a remarkable impact in medicinal, agrochemical, and materials science research. However, our inability to facilely incorporate the OCF3 group into molecules, especially heteroaromatics, has limited its potential across a broad spectrum of technological applications. Herein, we report a scalable and operationally simple protocol for regioselective trifluoromethoxylation of a wide range of functionalized pyridines and pyrimidines under mild reaction conditions. The trifluoromethoxylated products are useful scaffolds that can be further elaborated by amidation and palladium-catalysed cross coupling reactions. Mechanistic studies suggest that a radical O-trifluoromethylation followed by the OCF3-migration reaction pathway is operable. Given the unique properties of the OCF3 group and the ubiquity of pyridine and pyrimidine in biologically active molecules and functional materials, trifluoromethoxylated pyridines and pyrimidines could serve as valuable building blocks for the discovery and development of new drugs, agrochemicals, and materials.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Access to a new class of synthetic building blocks via trifluoromethoxylation of pyridines and pyrimidines

Feng

Lee

et al. 2016

Chem. Sci.

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“…However, inconsistent results are sometimes obtained even for the conformational property of relatively simple molecules. For example, there have been studies with slightly different conclusions as for the existence of the second conformer for , , -trifluoroanisol [1,2].…”

Section: Introductionmentioning

confidence: 99%

Conformational property of ethoxybenzene as studied by laser-jet spectroscopy and theoretical calculations

Egawa

Yamamoto

Daigoku

2010

Journal of Molecular Structure

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The conformational property of ethoxybenzene has been investigated by means of the laser-jet spectroscopy and the theoretical calculations. The quantum-mechanical analysis of the two-dimensional potential surfaces for the S 0 and S 1 states that have been obtained from the DFT and TDDFT calculations, respectively, has been carried out. Its result suggested the existence of the second conformer (gauche) in addition to the main conformer (trans) in the both states, and it was predicted that the 0-0 band of the gauche conformer would appear at about 400 cm -1 lower than that of the trans conformer. The S 1 ← S 0 fluorescence excitation spectrum of jet-cooled ethoxybenzene has been measured. The peak that is assignable to the 0-0 band of the second conformer has been observed, whose spectral position (red-shifted from that of the trans conformer for about 229 cm -1 ) is qualitatively consistent with the theoretical prediction.

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“…Fluorination of the methyl group has a strong effect on the conformation of anisole. In trifluoromethoxybenzene (a,a,a-trifluoroanisole) [9,10] and in p-fluoro(trifluoromethoxy)benzene (4,a,a,a-tetrafluoroanisole) [11] the CF 3 group is oriented perpendicular to the plane of the benzene ring (t(C2C1-OC) = 908). A small contribution of a planar conformer cannot definitely be excluded.…”

Section: Introductionmentioning

confidence: 99%