Repurposing of F-gases: challenges and opportunities in fluorine chemistry

Sheldon, Daniel; Crimmin, Mark R.

doi:10.1039/d1cs01072g

Cited by 42 publications

(26 citation statements)

References 254 publications

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“…The subsequent proposal to study the preferred route, involving the migration of a methyl group, is motivated by the desire to form more aromatic products. This investigation extends the field of main-group chemistry to the activation of CF 4 , similar to the activation of other super greenhouse gases (e.g., SF 6 , − hydrofluorocarbons). We hope these findings will provide guidelines for the activation of CF 4 and other super greenhouse gases.…”

Section: Discussionmentioning

confidence: 68%

Rational Design to Activate Tetrafluoromethane by Two-Coordinate Borinium

Huang

Yan

2023

Inorg. Chem.

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The activation of tetrafluoromethane (CF 4 ) is quite challenging. The current methods have a high decomposition rate but are expensive, and therefore, their widespread use is limited. Here, inspired by the successful C−F activation within saturated fluorocarbons, we have designed a rational approach based on two-coordinate borinium for activating CF 4 using density functional theory (DFT) calculations. Our calculations predict that this approach is both thermodynamically and kinetically favorable.

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Section: Discussionmentioning

confidence: 68%

Rational Design to Activate Tetrafluoromethane by Two-Coordinate Borinium

Huang

Yan

2023

Inorg. Chem.

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“…In pharmaceutical and agrochemical studies, the use of fluorine-containing molecular units becomes an essential approach, − and thus the synthesis of fluorinated phenanthridines has been quite important. Difluoromethyl (CF 2 H) has been an attractive fluoroalkyl group as a lipophilic bioisostere for hydroxy (OH), amino (NH 2 ), and thiohydroxy (SH) groups. , Table shows the reported synthesis of 6-(difluoromethyl)phenanthridines via radical isonitrile insertion.…”

Section: Introductionmentioning

confidence: 99%

Difluoromethylborates and Muonium for the Study of Isonitrile Insertion Affording Phenanthridines via Imidoyl Radicals

Konagaya,

Huang,

Iwami

et al. 2023

J. Org. Chem.

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The 6-(difluoromethyl)phenanthridine unit is a highly attractive fluoroalkyl-substituted planar nitrogen heterocycle in pharmaceutical and agrochemical research. In this paper, we report that difluoromethylborates can be used as a source of difluoromethyl radicals for isonitrile insertion, leading to 6-(difluoromethyl)phenanthridines. Tuning the aryl substituents in the difluoromethylborates and oxidizing reagents enabled the synthesis of 6-(difluoromethyl)phenanthridines through the generation of difluoromethyl radical and spontaneous intramolecular cyclization of the CF 2 H-imidoyl radical intermediates. The presence of difluoromethyl radicals was experimentally confirmed, and the reaction mechanisms including imidoyl radical and prompt cyclization reactions could be supported theoretically. Furthermore, we obtained valuable information about the imidoyl radical intermediate by performing transverse-field muon spin rotation (TF-μSR) measurements of 2-isocyano-4′-methoxy-1,1′-biphenyl and using density functional theory (DFT) calculations to interpret the spectra. Muonium, a simple free radical, preferentially adds to the carbon atom of the isonitrile unit, yielding the corresponding imidoyl radical. The temperature dependence of the muon hyperfine coupling constant and the spin relaxation of the muoniated radical signal are compatible with the intramolecular cyclization of biaryl-substituted imidoyl radicals on the μs time scale.

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“…5,6 Thus, selective activation of a single C-F bond in a trifluoromethyl (CF 3 ) group remains challenging. 7 Transition metal catalysed C(sp 3 )-F activation for the synthesis of organofluorinated derivatives has attracted increasing attention and achieved promising progress in recent decades. 8,9 In 2017, the Ko ¨nig group disclosed the first single C(sp 3 )-F functionalization of trifluoromethylarenes via a fac-Ir(ppy) 3 photocatalyst merged with Lewis acid activation, which showed good chemoselectivity control and functional group tolerance.…”

mentioning

confidence: 99%

“…5,6 Thus, selective activation of a single C–F bond in a trifluoromethyl (CF 3 ) group remains challenging. 7…”

mentioning

confidence: 99%

Photocatalytic C–F alkylation of trifluoromethyls using o-phosphinophenolate: mechanistic insights and substrate prediction

Li¹,

Yang²,

Guan³

2023

Chem. Commun.

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Repurposing of F-gases: challenges and opportunities in fluorine chemistry

Abstract: The applications, environmental issues, and methods for remediation of F-gases are reviewed.

Cited by 42 publications

References 254 publications

Rational Design to Activate Tetrafluoromethane by Two-Coordinate Borinium

Rational Design to Activate Tetrafluoromethane by Two-Coordinate Borinium

Difluoromethylborates and Muonium for the Study of Isonitrile Insertion Affording Phenanthridines via Imidoyl Radicals

Photocatalytic C–F alkylation of trifluoromethyls using o-phosphinophenolate: mechanistic insights and substrate prediction

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