Search results for "arylation"
showing 10 items of 13 documents
C-H Bond Arylation of Pyrazoles at the β-Position: General Conditions and Computational Elucidation for a High Regioselectivity
2021
International audience; Direct arylation of most five-membered ring heterocycles are generally easily accessible and strongly favored at the α-position using classical palladium-catalysis. Conversely, regioselective functionalization of such heterocycles at the concurrent β-position remains currently very challenging. Herein, we report general conditions for regioselective direct arylation at the β-position of pyrazoles, while C-H α-position is free. By using aryl bromides as the aryl source and a judicious choice of solvent, the arylation reaction of variously N-substituted pyrazoles simply proceeds via β-C-H bond functionalization. The β-regioselectivity is promoted by a ligand-free palla…
Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquino…
2017
International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…
Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfo…
2018
International audience; We provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium-1,1'-bis [(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium catalyzed C-S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C-S coupling. We established herein…
Cyclometalated Au(III) Complexes for Cysteine Arylation in Zinc Finger Protein Domains: Towards Controlled Reductive Elimination
2019
With the aim of exploiting the use of organometallic species for the efficient modification of proteins through C-atom transfer, the gold-mediated cysteine arylation through a reductive elimination process occurring from the reaction of cyclometalated AuIII C^N complexes with a zinc finger peptide (Cys2His2 type) is here reported. Among the four selected AuIII cyclometalated compounds, the [Au(CCON)Cl2] complex featuring the 2-benzoylpyridine (CCON) scaffold was identified as the most prone to reductive elimination and Cys arylation in buffered aqueous solution (pH 7.4) at 37 °C by high-resolution LC electrospray ionization mass spectrometry. DFT and quantum mechanics/molecular mechanics (Q…
(2-Pyridyl)sulfonyl Groups for ortho -Directing Palladium- Catalyzed Carbon-Halogen Bond Formation at Functionalized Arenes
2017
International audience; We describe an efficient palladium-catalyzed selective C-H ortho-monohalogenation (X=I, Br, Cl, F) of various functionalized (2-pyridyl) aryl-sulfones. ortho-, meta-and para-functionalization is tolerated at the arene group which undergoes C-H halogenation. Some modifications are also possible on the 2-(arylsulfonyl) heteroaryl directing groups. A comparison of the halogenation efficiency suggests that bromination is the practical method of choice, while chlorination and fluorination are possible but more challenging. Under forcing conditions ortho-dihalogenation can also be achieved.
Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au III Compounds: New Mechanistic Insights
2020
To gain more insight into the factors controlling the efficient cysteine arylation by cyclometalated Au(III) complexes, the reaction between selected gold compounds and different peptides was investigated by high‐resolution liquid chromatography electrospray ionization mass spectrometry (HR‐LC‐ESI‐MS). The deducted mechanisms of C–S cross‐coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.
New Internal-Charge-Transfer Second-Order Nonlinear Optical Chromophores Based on the Donor Ferrocenylpyrazole Moiety
2016
A series of new N-arylated ferrocenepyrazole structures, carrying different donor or acceptor substituents in the para position of the aryl ring, has been synthesized by the Chan-Lam cross-coupling reaction. The nonplanar geometric molecular structure of some of these chromophores together with their crystal packing was determined by X-ray diffraction, and the HOMO and LUMO energy levels were evaluated by electrochemical and optical measurements and by density functional theoretical (DFT) calculations. By the investigation of solvent effects and time-dependent DFT (TD-DFT) calculations, the intense electronic absorption band around 270-310 nm was confirmed to be an internal-chargetransfer (…
Defying Stereotypes with Nanodiamonds: Stable Primary Diamondoid Phosphines
2016
International audience; Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phosphines. The prepared primary diamantyl phosphines are quite air stable compared to their adamantyl and especially alkyl or aryl analogues. This finding is corroborated by comparing the singly occupied molecular orbital energy levels of the corresponding phosphine radical cations obtained by density functional theory computations.
Synthesis of fluorinated first generation starburst molecules containing a triethanolamine core and 1,2,4-oxadiazoles
2006
Abstract 5-Pentafluorophenyl-1,2,4-oxadiazoles, differently substituted at C(3), have been synthesized and used to functionalize the aliphatic primary hydroxyl functionalities of triethanolamine, under mild conditions. UV–visible absorption and emission spectra are reported, for both tri- and difunctionalised molecules, showing their potential applications as light-emitters in optoelectronic devices.
Palladium-Catalysed Intermolecular Direct C–H Bond Arylation of Heteroarenes with Reagents Alternative to Aryl Halides: Current State of the Art
2022
Abstract: This unprecedented review with 322 references provides a critical up-to-date picture of the Pd-catalysed intermolecular direct C–H bond arylation of heteroarenes with arylating reagents alternative to aryl halides that include aryl sulfonates (aryl triflates, tosylates, mesylates, and imidazole-1-sulfonates), diaryliodonium salts, [(diacetoxy)iodo]arenes, arenediazonium salts, 1-aryltriazenes, arylhydrazines and N’-arylhydrazides, arenesulfonyl chlorides, sodium arenesulfinates, arenesulfinic acids, and arenesulfonohydrazides. Particular attention has been paid to summarise the preparation of the various arylating reagents and to highlight the practicality, versatility, and limit…