Perhaloketones. XV. Preparation and some reactions of perhalocyclopentanones and -hexanones

Anello, Louis G.; Price, Anthony; Sweeney, Richard F.

doi:10.1021/jo01271a017

Cited by 8 publications

(4 citation statements)

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“…A mixture of the alkene (3) (2.13 g, 6.6 mmol) and bromine (1.05 g, 6.6 mmol) was left at room temperature for 24 h and then heated at 60 "C for a further 4 h to give a colourless liquid which on distillation yielded 1,l'dibromotetradecajuorobicyclobutyl(l3) ( have also described the direct use of solid calcium 30.7 mmol), and acetonitrile (15 ml) was stirred at room temperature for 48 h. Volatile material was transferred in vacuo to a cold trap and the resulting lower layer purified by preparative scale g.1.c. 14 and 19F n.m.r.…”

Section: Reactions Of Perjuorobicyclobutylidenementioning

confidence: 97%

Reactions involving fluoride ion. Part 31. Remarkable reactivity of perfluoro-bicyclobutylidene

Bayliff¹,

Chambers²,

KIRK³

et al. 1985

J. Chem. Soc., Perkin Trans. 1

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~ Perfluorobicyclobutylidene (3) readily forms cycloadducts with butadiene, cyclopentadiene, 6,6dimet hylfu lvene and furan, whereas perf1 uoro-3,4-dimethyl hex-2-ene (2) is unreactive under the same conditions. This marked difference in reactivity between (2) and (3) is attributed to angle strain in (3). Reaction of the alkene (3) with cyclohexa-I ,3-diene yields 1 H,l 'H-perfluorobicyclobutyl (9) and benzene, by hydrogen transfer. The alkene (3) undergoes an 'ene' reaction with propene. Epoxides of perfluorobicyclobutylidene (3) and perfluorobicyclopentylidene (1 1 ) have been prepared; they both show high thermal stability and the latter epoxide fragments in the presence of fluoride ion t o yield perfluorocyclopentene and perfluorocyclopentanone. Part 31, ref. 15.

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Section: Reactions Of Perjuorobicyclobutylidenementioning

confidence: 97%

Reactions involving fluoride ion. Part 31. Remarkable reactivity of perfluoro-bicyclobutylidene

Bayliff¹,

Chambers²,

KIRK³

et al. 1985

J. Chem. Soc., Perkin Trans. 1

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“…An alternative (and much shorter) approach to perfluorocycloalkanones 381 and 382 was also based on nucleophilic epoxide ring opening. [276] In this case, epoxidation of alkenes 377 or 396 was followed by reaction with KF (Scheme 111); with 377 as the starting material, nucleophilic substitution also occurred at the last step. A general approach to the vicinally fluorinated cycloalkane derivatives includes fluoride-induced epoxide ring opening followed by direct or indirect nucleophilic fluorination at the OH group formed.…”

Section: Synthesis Of Other Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

“…An alternative (and much shorter) approach to perfluorocycloalkanones 381 and 382 was also based on nucleophilic epoxide ring opening [276] . In this case, epoxidation of alkenes 377 or 396 was followed by reaction with KF (Scheme 111); with 377 as the starting material, nucleophilic substitution also occurred at the last step.…”

Section: Synthesis Of Other Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

“…Nucleophilic chloride – fluoride exchange was the last step in the reaction sequence used to obtain perfluorinated ketones 381 and 382 starting from perhalogenated alkenes 377 (Scheme 107). [276] Compounds 381 and 382 were used to obtain some other building blocks including alcohols 383 [276] and amine 384 [277] (Scheme 108). Interestingly, ketone 382 gave adduct with Me 4 N + F − that was transformed hydrate 386 upon treatment with concentrated H 2 SO 4 (so that dehydration of H 2 SO 4 formally occurred) (Scheme 109).…”

Section: Synthesis Of Other Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

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Fluorinated Cycloalkyl Building Blocks for Drug Discovery

et al. 2022

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The review covers various aspects of fluorinated cycloalkyl (C3−C7) building blocks for drug discovery, including their synthesis, key physicochemical properties, and biological and medicinal applications of their derivatives. The discussed synthetic methods include classical nucleophilic fluorinations of various substrates, the addition of fluorine and another heteroatom to double bonds, cycloadditions and other transformations of fluorine‐containing substrates, as well as some newer reactions like fluorination of non‐activated and remotely activated C−H bonds, decarboxylative and deborylative fluorinations, etc. The known data on the effect of introducing the fluorinated cycloalkyl groups on the compound's key in vitro parameters (such as acidity/basicity, lipophilicity, conformational behavior, and short contact capabilities) are surveyed. Finally, applications of fluorinated cycloalkyl building block derivatives in the design of biologically active compounds (including marketed drugs Maraviroc, Ivosidenib, and Sitafloxacin) are covered, with a focus on the fluorination impact.

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Liquid-phase photofluorination with elemental fluorine. Part III. Synthesis of perfluorocycloalkyl ethers with/without a chlorine substituent

Ono¹,

Yamanouchi²,

Fernandez³

et al. 1995

Journal of Fluorine Chemistry

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Perhaloketones. XV. Preparation and some reactions of perhalocyclopentanones and -hexanones

Cited by 8 publications

References 0 publications

Reactions involving fluoride ion. Part 31. Remarkable reactivity of perfluoro-bicyclobutylidene

Reactions involving fluoride ion. Part 31. Remarkable reactivity of perfluoro-bicyclobutylidene

Fluorinated Cycloalkyl Building Blocks for Drug Discovery

Liquid-phase photofluorination with elemental fluorine. Part III. Synthesis of perfluorocycloalkyl ethers with/without a chlorine substituent

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