Convenient synthesis of fluorinated alkanes and cycloalkanes by hydrogenation of perfluoroalkylalkenes under ultrasound irradiation

Carcenac, Yvan; Tordeux, Marc; Wakselman, Claude; Diter, Patrick

doi:10.1016/j.jfluchem.2005.07.006

Cited by 25 publications

(42 citation statements)

References 29 publications

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“…The CF 3 –C1 bond adopts a perfectly staggered conformation in this structure. This assignment corrects the earlier literature, 48 focuses attention on the ambiguities arising from the assignment of configuration in such α-trifluoromethyl tertiary alcohols on the basis of chemical shift arguments alone, and underlines the need for unambiguous methods for assignment of configuration that are preferably based on the analysis of coupling constants.…”

Section: Resultssupporting

confidence: 69%

“…Previously, the major product from the reaction with 4-phenylcyclohexanone was assigned the opposite configuration (CF 3 trans to phenyl) on the basis of chemical shift differences in the derived xanthate esters of the two isomers. 48 In view of this discrepancy and in support of the FDCS NMR method discussed below, we obtained an X-ray crystal structure of the major isomer from reaction with 4-phenylcyclohexane ( Supporting Information and CCDC 1032684), which confirms its chair conformation and the axial location of the CF 3 group. The CF 3 –C1 bond adopts a perfectly staggered conformation in this structure.…”

Section: Resultsmentioning

confidence: 93%

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Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

et al. 2015

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The synthesis of a series of α-trifluoromethylcyclohexanols and analogous trimethylsilyl ethers by addition of the Ruppert-Prakash reagent to substituted cyclohexanones is presented. A method for the assignment of configuration of such compounds and of related α-trifluoromethylcyclohexylamines and of quaternary trifluoromethyl-substituted carbons is described based on the determination of the 3JCH coupling constant between the fluorine decoupled 13CF3 resonance and the vicinal hydrogens. This method is dubbed Fluorine-Decoupled Carbon Spectroscopy and abbreviated FDCS. The method is also applied to the configurational assignment of substances bearing mono-, di-, and perfluoroalkyl rather than trifluoromethyl groups. The configuration of all substances was verified by either 1H,19F heteronuclear Overhauser spectroscopy (HOESY) or by X-ray crystallography. The relative merits of FDCS and HOESY are compared and contrasted. 2JCH, 3JCH, and 4JCH to 19F decoupled CF3 groups in alkenes and arenes have also been determined and should prove useful in the structural assignment of trifluoromethylated alkenes and arenes.

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Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 93%

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

et al. 2015

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“…40 Elimination of the tertiary hydroxyl group from compound 28 was performed following a procedure by Diter and co-workers. 41 …”

Section: Resultsmentioning

confidence: 99%

Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts

Dibble

Woerpel

2011

J. Org. Chem.

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The axial conformer of several 4-substituted cyclohexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that was consistent with electrostatic stabilization of the axial conformer. 1 H NMR spectroscopic analysis was utilized to determine the structure of cyclohexanone-derived substrates by comparison to conformationally restricted transdecalone derivatives and computational models. X-ray crystallography demonstrated that the axial configuration of a pendant benzyloxy group is the preferred conformation of an iminium ion in the solid state. The structure of a neutral hydrazone was also determined to favor the axial configuration for a pendant benzyloxy group in the solid state.

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“…8 Both stereoisomer's cis and trans 1-trifluoromethyl-4-tert butylcyclohexane rings are considered as not flexible; other values are compared to the spectrum values of these two Scheme 1. carbon numbering of cis and trans 1,4 disubstituted cyclohexanes. cis compounds were compared to both conformers of alkyl and phenyl monosubstituted cyclohexane with the substituent in an axial or equatorial position.…”

Section: Resultsmentioning

confidence: 99%

“…The studied compounds were already described. 8 The assignment of the 13 C NMR signal proceeded from the C-F coupling constants, DEPT, HCOR and JMOD experiments.…”

Section: Methodsmentioning

confidence: 99%

Influence of the spatial position of a trifluoromethyl group on the ¹³C chemical shifts in the cyclohexane series

Carcenac

Diter

Wakselman

et al. 2006

Magnetic Reson in Chemistry

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The influence of the introduction of a trifluoromethyl group on the 13C chemical shifts in cyclohexane was examined. The two main effects observed are located at the alpha and gamma positions relative to the carbon bearing the fluorine atoms. By comparison of the collected data it was possible to calculate the increments corresponding to the substitution of a hydrogen atom by a CF3 group at axial or equatorial positions on the cyclohexane ring.

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Convenient synthesis of fluorinated alkanes and cycloalkanes by hydrogenation of perfluoroalkylalkenes under ultrasound irradiation

Cited by 25 publications

References 29 publications

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts

Influence of the spatial position of a trifluoromethyl group on the ¹³C chemical shifts in the cyclohexane series

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Convenient synthesis of fluorinated alkanes and cycloalkanes by hydrogenation of perfluoroalkylalkenes under ultrasound irradiation

Cited by 25 publications

References 29 publications

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with19F–1H Heteronuclear Overhauser Effect Spectroscopy

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with19F–1H Heteronuclear Overhauser Effect Spectroscopy

Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts

Influence of the spatial position of a trifluoromethyl group on the 13C chemical shifts in the cyclohexane series

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Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with¹⁹F–¹H Heteronuclear Overhauser Effect Spectroscopy

Influence of the spatial position of a trifluoromethyl group on the ¹³C chemical shifts in the cyclohexane series