2248-17-1

Upstream product

• 312-68-5 3-fluoropropyl tosylate 
• 41865-47-8 2-<(2-tetrahydropyranyl)oxy>-2-phenylacetonitrile 
• 935-64-8 1-phenyl-1-cyclobutanol 
• 1007-70-1 Methyl(1-phenylcyclobutyl)ether 
• 373-53-5 fluoroiodomethane 
• 768-03-6 Phenyl vinyl ketone 

Downstream Products

• 98-86-2 acetophenone 

Relevant academic research and scientific papers

Photoreactivity of α-Fluorinated Phenyl Alkyl Ketones

The photoreactivities of the mono-, di-, and tri-α-fluorinated acetophenones have been compared to that of acetophenone itself.All four ketones have similar triplet excitation energies; the three fluorinated ketones have reduction potentials 0.5-0.7 eV lower than that of acetophenone.Triplet reactivity toward alkylbenzenes keeps increasing with fluorine substitution, Since the rate-determining step becomes charge-transfer complexation as the ketone reduction potential decreases.The primary/tertiary C-H selectivity toward p-cymene increases with the number of fluorines.Triplet reactivity toward cyclopentane also is increased by fluorination but peaks at two fluorines, since the lowest triplet switches from n,?* to ?,?* with two or three fluorines and ?,?*triplets are unreactive in simple hydrogen atom abstraction.In contrast, α-fluorination of valerophenone does not significantly increase the rate of triplet γ-hydrogen abstraction.The inductive effect on reactivity apparently is offset by a conformational effect.Th α-fluorinated phenones give predominantly cyclobuthanols instead of Norrish type II elimination. α-fluoroacetophenone forms predominantly acetophenone and HF when irradiated with 2-propanol, in what appears a short chain process involving electron transfer to ketone followed by fluoride ion loss.Finally, the radical coupling products in these reactions are formed in varying yields, depending on solvent and additives.It is suggested that radical solvation can affect radical coupling rates sufficiently to prevent statistical ratios of cross-coupling and homo-coupling.

Ring-opening fluorination of cyclobutanols and cyclopropanols catalyzed by silver

Cyclobutanols and cyclopropanols underwent ring-opening fluorination upon treatment with Selectfluor in the presence of a substoichiometric amount of a silver salt. The reaction provides an efficient method to synthesize γ- and β-fluoroalkyl ketones.

C-C Bond Fluorination via Manganese Catalysis

β- and γ-fluorinated ketones are desirable moieties in building blocks for bioactive molecules. Recent progress in installing this functionality has centered around ring-opening carbon-carbon bond cleavage/fluorination of strained cycloalkanols, either us

Visible light-mediated radical fluoromethylation: Via halogen atom transfer activation of fluoroiodomethane

Incorporation of the fluoromethyl group can profoundly influence the physicochemical properties of organic molecules, offering a promising strategy for the discovery of novel pharmaceutical agents. Direct fluoromethylation of unfunctionalized C(sp2) centres can be achieved using fluoromethyl radicals, but current methods for their generation usually rely on the activation of non-commercial or expensive radical precursors via inefficient single electron transfer pathways, which limits their synthetic application. Here we report the development of a fluoromethylation strategy based on the generation of fluoromethyl radicals from commercially available fluoroiodomethane via halogen atom transfer. This mode of activation is orchestrated by visible light and tris(trimethylsilyl)silane, which serves as both a hydrogen- and halogen atom transfer reagent to facilitate the formation of C(sp3)-CH2F bonds via a radical chain process. The utility of this metal- and photocatalyst-free transformation is demonstrated through the multicomponent synthesis of complex α-fluoromethyl amines and amino acid derivatives via radical addition to in situ-formed iminium ions, and the construction of β-fluoromethyl esters and amides from electron-deficient alkene acceptors. These complex fluoromethylated products, many of which are inaccessible via previously reported methods, may serve as useful building blocks or fragments in synthetic and medicinal chemistry both in academia and industry. This journal is

Rapid and scalable synthesis of fluoroketonesviacerium-mediated C-C bond cleavage

Ketones with remote fluorination are an important motif in the synthesis of bioactive molecules. Here we demonstrate that ceric ammonium nitrate (CAN) is able to produce this functionality under incredibly mild conditions and short reaction times (30 min)

Silver-Catalyzed Ring-Opening Strategy for the Synthesis of β- and γ-Fluorinated Ketones

A regioselective synthesis of β- and γ-fluorinated ketones via silver-catalyzed ring opening is described. A variety of β- and γ-fluorinated ketones are efficiently prepared, respectively, from tertiary cyclopropanol and cyclobutanol precursors, providing a straightforward approach for the introduction of a fluorine atom into complex molecules. Preliminary mechanistic studies suggest that a radical-mediated sequential C-C bond cleavage and C-F bond formation pathway is involved.

Iron- or silver-catalyzed oxidative fluorination of cyclopropanols for the synthesis of β-fluoroketones

The FeIII- or AgI-catalyzed oxidative fluorination of cyclopropanols via radical rearrangement is disclosed. This process features a straightforward and highly effective protocol for the site-specific synthesis of β-fluoroketones and represents an expedient method for the synthesis of γ-, δ- and ε-fluoroketones. Notably, this reaction proceeds at room temperature and tolerates a diverse array of cyclopropanols.