19031-66-4

Upstream product

• 2550-26-7 4-Phenyl-2-butanone 
• 917-54-4 methyllithium 
• 103-05-9 4-phenyl-2-methyl-2-butanol 
• 1361152-14-8 tert-butyl 2,2-dimethyl-4-phenylbutaneperoxoate 
• 52017-21-7 (3-bromo-3-methyl-n-butyl)benzene 
• 6683-51-8 2-methyl-4-phenyl-1-butene 

Downstream Products

• 4830-95-9 2-chloro-2-methyl-4-phenylbutane 
• 17314-92-0 (3,3-dimethylbutyl)benzene 
• 52356-07-7 3.3-Dimethyl-1-phenyl-pentan 
• 32366-28-2 (3-azido-3-methyl-butyl)-benzene 
• 828282-52-6 (1,1-dimethyl-3-phenylpropyl)diphenylphosphine 
• 1032065-06-7 2-(1,3-cyclopentadienyl)-2-methyl-4-phenylbutane 
• 1032065-04-5 2-(1,4-cyclopentadienyl)-2-methyl-4-phenylbutane 
• 1032065-15-8 (3-cyclopentyl-3-methylbutyl)benzene 
• 79399-21-6 (2-methyl-4-phenylbutan-2-yl)(phenyl)sulfane 

Relevant academic research and scientific papers

Dehydroxylative Fluorination of Tertiary Alcohols

A large number of fluorination methods have been developed, but the construction of a tertiary C-F bond remains challenging. Herein, we describe an efficient dehydroxylative fluorination of tertiary alcohols with Selectfluor via the activation of a hydroxyl group by a Ph2PCH2CH2PPh2/ICH2CH2I system. Although the reagents appear to be not compatible (Selectfluor with the phosphine and I- generated in situ), the reactions occur rapidly to give the desired products in moderate to high yields. This work may present a new discovery in fluorination of alcohols since the reported methods are mainly limited to primary and secondary alcohols.

Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

We report a redox-neutral method for nucleophilic fluorination of N-hydroxyphthalimide esters using an Ir photocatalyst under visible light irradiation. The method provides access to a broad range of aliphatic fluorides, including primary, secondary, and tertiary benzylic fluorides as well as unactivated tertiary fluorides, that are typically inaccessible by nucleophilic fluorination due to competing elimination. In addition, we show that the decarboxylative fluorination conditions are readily adapted to radiofluorination with [18F]KF. We propose that the reactions proceed by two electron transfers between the Ir catalyst and redox-active ester substrate to afford a carbocation intermediate that undergoes subsequent trapping by fluoride. Examples of trapping with O- and C-centered nucleophiles and deoxyfluorination via N-hydroxyphthalimidoyl oxalates are also presented, suggesting that this approach may offer a general blueprint for affecting redox-neutral SN1 substitutions under mild conditions.

Predictable site-selective radical fluorination of tertiary ethers

In this communication, we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers, enabled by synergistic photocatalysis and organocatalysis. This catalytic combination allows for exclusi

Nickel-Catalyzed Hydrofluorination of Unactivated Alkenes through a HAT Pathway

We report the hydrofluorination of unactivated alkenes using N-fluorobenzenesulfonimide as a fluorination reagent. The reaction produces exclusively Markovnikov hydrofluorination products under mild conditions. It is not affected by air or moisture and us

Light-Mediated Formal Radical Deoxyfluorination of Tertiary Alcohols through Selective Single-Electron Oxidation with TEDA2+.

The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of C?F bonds from (hetero)benzylic, propargylic, and non-activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single-electron oxidation of cesium oxalates—which are readily available from the corresponding tertiary alcohols—with in situ generated TEDA2+. (TEDA: N-(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor.

Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates

A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon–fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2, resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.

Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor

Herein we disclose a deoxyfluorination of alcohols with an electrophilic fluorine source via visible-light photoredox catalysis. This radical-mediated C–F coupling is capable of fluorinating secondary and tertiary alcohols efficiently, complementing previously reported nucleophilic deoxyfluorination protocols.

Direct Hydrofluorination of Methallyl Alkenes Using a Methanesulfonic Acid/Triethylamine Trihydrofluoride Combination

The use of a methanesulfonic acid/triethylamine trihydrofluoride combination for the direct hydrofluorination of methallyl-containing substrates is reported. Under those metal-free conditions that use readily available, cheap, and easy to handle reagents,

Ligand-Promoted Iron(III)-Catalyzed Hydrofluorination of Alkenes

An iron-catalyzed hydrofluorination of unactivated alkenes has been developed. The use of a multidentate ligand and the fluorination reagent N-fluorobenzenesulfonimide (NFSI) proved to be critical for this reaction, which afforded various fluorinated comp

Selective Radical Fluorination of Tertiary Alkyl Halides at Room Temperature

Direct fluorination of tertiary alkyl bromides and iodides with Selectfluor is described. The halogen-exchange fluorination proceeds efficiently in acetonitrile at room temperature under metal-free conditions and exhibits a wide range of functional group compatibility. Furthermore, the reactions are highly selective in that alkyl chlorides and primary and secondary alkyl bromides remain intact. A radical mechanism is proposed for this selective fluorination.