Absolute rate constants for some hydrogen atom abstraction reactions by a primary fluoroalkyl radical in waterElectronic supplementary information (ESI) available: Tables of kinetic data and plots of kinetic data. See http://www.rsc.org/suppdata/ob/b3/b313757k/

Zhang, Li; Cradlebaugh, Joseph A.; Litwinienko, Grzegorz; Smart, Bruce E.; Ingold, K. U.; Dolbier, William R. Jr.

doi:10.1039/b313757k

Cited by 15 publications

(14 citation statements)

References 24 publications

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“…Further transformation of the difluoroiodomethyl group of 2a was achieved by heating ( Scheme 3 ). Thus, refluxing a DMF solution of 2a for 15 h induced iodine–hydrogen exchange to afford difluoromethylated dihydrophenanthrene derivative 4a in almost quantitative yield [ 29 – 30 ]. A difluoromethyl group functions as a hydrogen-bond donor and a bioisostere of a hydroxy group, as a result of which difluoromethyl-bearing compounds attract much attention as bioactive materials [ 31 – 32 ].…”

Section: Resultsmentioning

confidence: 99%

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

Fujita

Kinoshita

Takanohashi

et al. 2017

Beilstein J. Org. Chem.

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1,1-Difluoro-1-alkenes bearing a biaryl-2-yl group effectively underwent site-selective intramolecular iodoarylation by the appropriate cationic iodine species. Iodoarylation of 2-(2-aryl-3,3-difluoroallyl)biaryls proceeded via regioselective carbon–carbon bond formation at the carbon atoms in β-position to the fluorine substituents, thereby constructing dibenzo-fused six-membered carbocycles bearing a difluoroiodomethyl group. In contrast, 2-(3,3-difluoroallyl)biaryls underwent a similar cyclization at the α-carbon atoms to afford ring-difluorinated seven-membered carbocycles.

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Section: Resultsmentioning

confidence: 99%

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

Fujita

Kinoshita

Takanohashi

et al. 2017

Beilstein J. Org. Chem.

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“…Hydrogen abstractions from ethers did not show a significant solvent effect. 15 Rate constants for H-abstraction from alkoxides were 100-1000 times greater than for the corresponding alcohols. 16 Isotope effects measured in water suggested tunnelling might be important.…”

Section: Miscellaneous Hydrogen Abstractionsmentioning

confidence: 94%

11 Reaction mechanisms : Part (i) Radical and radical ion reactions

Tanko

2005

Annu. Rep. Prog. Chem., Sect. B

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“…The deuterated product 2′ was not detected (Scheme ). However, this result can be explained by the strong isotope effect (the rate of a hydrogen abstraction from THF by carbon‐centered radicals is approximately 8 times faster than a deuterium abstraction from [D 8 ]THF17).…”

Section: Methodsmentioning

confidence: 99%

“…Reaction conditions: reactor with mpg-C 3 N 4 (2.5 wt %), 1 (0.04 mmol), solvent (5 mL); t r = 5 min; F = 0.124 mL min À1 ; blue LED irradiation (l = 420-425 nm). strong isotope effect (the rate of a hydrogen abstraction from THF by carbon-centered radicals is approximately 8 times faster than a deuterium abstraction from [D 8 ]THF [17] ). The rate of hydrogen abstraction by an alkyl radical is found to correlate very well with the CÀH bond dissociation energy values (BDE) of H-donors.…”

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confidence: 99%

THF: An Efficient Electron Donor in Continuous Flow Radical Cyclization Photocatalyzed by Graphitic Carbon Nitride

Woźnica

Chaoui

Taabache

et al. 2014

Chemistry A European J

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Mesoporous graphitic carbon nitride (mpg-C3 N4 ) was found to be an efficient heterogeneous photocatalyst for the metal-free radical cyclization of 2-bromo-1,3-dicarbonyl compounds. Reactions leading to functionalized cyclopentanes proceed under mild conditions and can be conducted in a continuous flow photoreactor. Compared to the batch reaction, the use of a continuous flow reactor resulted in a significant reduction in reaction time (complete conversion of 0.04 mmol of substrate in a batch was achieved after 4 h, whereas in a flow reactor the same amount of substrate was fully converted into a product within 40 min). Mechanistic studies of the reaction showed that THF plays not only the role of solvent, but is also a crucial hydrogen and electron donor.

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Absolute rate constants for some hydrogen atom abstraction reactions by a primary fluoroalkyl radical in waterElectronic supplementary information (ESI) available: Tables of kinetic data and plots of kinetic data. See http://www.rsc.org/suppdata/ob/b3/b313757k/

Cited by 15 publications

References 24 publications

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

11 Reaction mechanisms : Part (i) Radical and radical ion reactions

THF: An Efficient Electron Donor in Continuous Flow Radical Cyclization Photocatalyzed by Graphitic Carbon Nitride

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