The Trifluoromethyl Group in Chemistry and Spectroscopy. Carbon—Fluorine Hyperconjugation

Stock, Leon M.; Wasielewski, Michael R.

doi:10.1002/9780470171929.ch4

Cited by 20 publications

(1 citation statement)

References 109 publications

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“…Electron-withdrawing CF 3 and COCF 3 lower the barriers by 5.8 and 8.0 kcal/mol, respectively, consistent with the electron-withdrawing nature of the substituents (σ R _CF 3 = 0.16 and σ R _COCF 3 = 0.26). 20 F is inductively electron-withdrawing (σ R _ F = −0.32), 21 but due to its resonance electron-donating nature, the reaction barrier is increased by 1.4 kcal/mol.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis

Xie

Liang

et al. 2022

J. Org. Chem.

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The importance of fluoro and trifluoromethyl substituents in drug effectiveness prompted the computational exploration of fluorine-containing substituents in valuable synthetic cycloadditions. Diels–Alder or 1,3-dipolar cycloaddition reactions of typical reactants, cyclopentadiene, N-phenyldiazoacetamide, tetrazine, and N-phenylsydnone involving fluorine-containing substituents (F, CF3, and COCF3) were studied with M06-2X density functional theory. Inductive and conjugative effects influence normal and inverse electron-demand reactions differently. These results provide a guide to the design and use of cycloadditions for the introduction of fluoro and trifluoromethyl substituents in synthetic processes.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis

Xie

Liang

et al. 2022

J. Org. Chem.

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Structural Principles of Unsaturated Organic Compounds: Evidence by Quantum Chemical Calculations

Dähne

Moldenhauer

1985

Progress in Physical Organic Chemistry

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Thermochemistry of Halogenated Organic Compounds*

Slayden¹,

Liebman²,

Mallard³

2009

Patai's Chemistry of Functional Groups

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Introduction Systematics of the Energetics of Alkyl Halides Thermochemical Mimicry of Alkyl and Aryl Halides Stabilization and Destabilization in Alkyl and Aryl Halides Acyl Halides On Route to Positive Halogen Thermochemistry of Highly Fluorinated Saturated Species Bond Energies and Radical Enthalpies of Formation A Brief Discussion of the Current Status of Computational Results

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The Trifluoromethyl Group in Chemistry and Spectroscopy. Carbon—Fluorine Hyperconjugation

Cited by 20 publications

References 109 publications

Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis

Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis

Structural Principles of Unsaturated Organic Compounds: Evidence by Quantum Chemical Calculations

Thermochemistry of Halogenated Organic Compounds*

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