477219-29-7

Upstream product

• 4476-28-2 (4-isopropylphenyl)acetic acid 
• 352-12-5 4-chlorobenzyl fluoride 
• 1068-55-9 isopropylmagnesium chloride 
• 99-87-6 4-methylisopropylbenzene 

Relevant academic research and scientific papers

Radical C-H Fluorination Using Unprotected Amino Acids as Radical Precursors

We report a unique example of utilizing unprotected amino acids for benzylic C-H fluorination via a radical process. α-Aminoalkyl radicals are readily generated via oxidative decarboxylation of unprotected amino acids using a simple silver(I) catalyst and Selectfluor, which serves as both a mild oxidant and source of electrophilic fluorine. Mechanistic investigation shows that coordination of the unprotected amino acid plays a crucial role in lowering the oxidation potential of Ag(I), enabling oxidation under mild conditions. Mono- or difluorination is possible by controlling the stoichiometry of amino acid and fluorine source.

Iron-Catalyzed Isopropylation of Electron-Deficient Aryl and Heteroaryl Chlorides

Traditional methods for the preparation of secondary alkyl-substituted aryl and heteroaryl chlorides challenge both selectivity and functional group tolerance. This contribution describes the use of statistical design of experiments to develop an effective procedure for the preparation of isopropyl-substituted (hetero)arenes with minimal isopropyl to n-propyl isomerization. The reaction tolerates electronically diverse aryl chloride coupling partners, with excellent conversion observed for strongly electron-deficient aromatic rings, such as esters and amides. Electron-rich systems, including methyl- and methoxy-substituted aryl chlorides, were found to be less reactive. Furthermore, the reaction was found to be most successful when heteroaryl chlorides were submitted to the cross-coupling protocol. By mapping substituent effects on reaction selectivity, we were able to show that electron-deficient aryl chlorides are essential for efficient coupling, and use electronic structure calculations to predict the likelihood of successful coupling through the estimation of the electron affinity of each aryl chloride. Moderate isolated yields were achieved with selected aryl chlorides, and moderate to good isolated yields were obtained for all the heteroaryl chlorides coupled. Excellent selectivity was observed when a 2,6-dichloroquinoline was used, allowing mono-substitution on a challenging substrate. (Figure presented.).

Photocatalyzed benzylic fluorination: Shedding "light" on the involvement of electron transfer

The photocatalyzed oxidation of benzylic compounds by 1,2,4,5-tetracyanobenzene (TCB) in the presence of Selectfluor provides a synthetically efficient route to electron deficient, less substituted, and otherwise inaccessible benzylic fluorides. The virtue of this system is multifold: it is metal-free and mild, and the reagents are inexpensive. Mechanistically, the data suggest the intimate formation of intermediate radical cations in the key radical forming step, as opposed to a concerted hydrogen atom transfer process.

Iron(II)-catalyzed benzylic fluorination

Direct C-F functionalization of benzylic sp3 C-H bonds is a synthetic challenge that has yet to be propitiously overcome. A mild, one-pot synthesis of monofluorinated benzylic substrates is reported with commercially available iron(II) acetylacetonate and Selectfluor in good to excellent yields and selectivity. A convenient route to β-fluorinated products of 3-aryl ketones is also highlighted, providing a synthetic equivalent to the difficult to accomplish conjugate addition of fluoride to α,β-unsaturated ketones.

Fluorodecarboxylation, rearrangement and cyclisation: the influence of structure and environment on the reactions of carboxylic acids with xenon difluoride

The reactions of structurally diverse carboxylic acids with XeF2 in both CH2Cl2/Pyrex and CH2Cl2/PTFE have been studied. Pyrex appears to be a very effective heterogeneous catalyst for an electrophilic mode of reaction of polarised XeF2, leading to rearrangement, cyclisation and cationic products. In CH2Cl2/PTFE, fluorodecarboxylation is the main mode of reaction, in accordance with previous studies, and may occur via a SET reaction of unpolarised XeF2.