Electrochemical ortho functionalization of 2-phenylpyridine with perfluorocarboxylic acids catalyzed by palladium in higher oxidation states

The electochemical oxidation of palladium acetate or palladium perfluoroacetate in the presence of 2-phenylpyridine promotes catalytic ortho C-H substitution reactions. As possible intermediates, Pd(II) metallacycles with Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents have been isolated and characterized: binuclear [(PhPy)Pd(μ-OAc)]2 and [(PhPy)Pd(μ-TFA)]2 and mononuclear [(PhPy)Pd(TFA)](CH 3CN), [(PhPy)Pd(TFA)](PhPy), and [(PhPy)Pd(PFH)](PhPy). The fluorinated derivatives were found to exist in solvent-dependent equilibria between mononuclear and binuclear forms. Cyclic voltammetry was used to elucidate redox properties of the palladacycles and the oxidation route to the final products. © 2013 American Chemical Society

Chiral thiophosphorylated thioureas: Synthesis, structure, and cyclization reaction

© 2014 Wiley Periodicals, Inc. A number of chiral racemic and enanthiopure thiophosphorylated thioureas were synthesized by the reaction of 2-aminobutan-1-ol and 1-(a-aminobenzyl)-2-naphthol with O,O-diethyl thiophosphoryl isothiocyanate. It was found that such thioureas undergo the cyclization reaction under basic conditions with hydrogen sulfide elimination and the formation of thiophosphorylated oxasines. XRay single crystal diffraction revealed that the structure of thiourea is close to the prereaction state of the cyclization reaction

Electrochemical ortho functionalization of 2-phenylpyridine with perfluorocarboxylic acids catalyzed by palladium in higher oxidation states

The electochemical oxidation of palladium acetate or palladium perfluoroacetate in the presence of 2-phenylpyridine promotes catalytic ortho C-H substitution reactions. As possible intermediates, Pd(II) metallacycles with Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents have been isolated and characterized: binuclear [(PhPy)Pd(μ-OAc)]2 and [(PhPy)Pd(μ-TFA)]2 and mononuclear [(PhPy)Pd(TFA)](CH 3CN), [(PhPy)Pd(TFA)](PhPy), and [(PhPy)Pd(PFH)](PhPy). The fluorinated derivatives were found to exist in solvent-dependent equilibria between mononuclear and binuclear forms. Cyclic voltammetry was used to elucidate redox properties of the palladacycles and the oxidation route to the final products. © 2013 American Chemical Society

Electrochemical ortho functionalization of 2-phenylpyridine with perfluorocarboxylic acids catalyzed by palladium in higher oxidation states

The electochemical oxidation of palladium acetate or palladium perfluoroacetate in the presence of 2-phenylpyridine promotes catalytic ortho C-H substitution reactions. As possible intermediates, Pd(II) metallacycles with Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents have been isolated and characterized: binuclear [(PhPy)Pd(μ-OAc)]2 and [(PhPy)Pd(μ-TFA)]2 and mononuclear [(PhPy)Pd(TFA)](CH 3CN), [(PhPy)Pd(TFA)](PhPy), and [(PhPy)Pd(PFH)](PhPy). The fluorinated derivatives were found to exist in solvent-dependent equilibria between mononuclear and binuclear forms. Cyclic voltammetry was used to elucidate redox properties of the palladacycles and the oxidation route to the final products. © 2013 American Chemical Society

Diastereoselective synthesis of α-aminoalkylphosphonic acid derivatives of Betti base

© 2014 Springer Science+Business Media New York. A reaction of triethyl phosphite with 3-alkyl-1-phenylnaphthoxazines in the presence of halotrimethylsilanes with subsequent removal of the trimethylsilyl group by hydrolysis furnished diastereomeric α-aminoalkylphosphonic derivatives of Betti base. The highest diastereomeric excess was observed in the reaction with bromotrimethylsilane at low temperature. In the case of 3-isobutyl-1-phenylnaphthoxazine, a major diastereomer was isolated from the reaction mixture by crystallization. X-ray diffraction analysis was used to establish relative configuration of its chiral centers. This method can be also used for the preparation of α-aminobenzylphosphonic derivatives, which was shown using 1,3-diphenylnaphthoxazine as an example. Major diastereomers of α-aminobenzyl- and α-aminoalkylphosphonic acid derivatives of Betti base obtained according to this procedure have different relative configurations of their chiral centers

France-soir

22 septembre 19461946/09/22 (A5,N696)-1946/09/23

Electrochemical ortho functionalization of 2-phenylpyridine with perfluorocarboxylic acids catalyzed by palladium in higher oxidation states

The electochemical oxidation of palladium acetate or palladium perfluoroacetate in the presence of 2-phenylpyridine promotes catalytic ortho C-H substitution reactions. As possible intermediates, Pd(II) metallacycles with Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents have been isolated and characterized: binuclear [(PhPy)Pd(μ-OAc)]2 and [(PhPy)Pd(μ-TFA)]2 and mononuclear [(PhPy)Pd(TFA)](CH 3CN), [(PhPy)Pd(TFA)](PhPy), and [(PhPy)Pd(PFH)](PhPy). The fluorinated derivatives were found to exist in solvent-dependent equilibria between mononuclear and binuclear forms. Cyclic voltammetry was used to elucidate redox properties of the palladacycles and the oxidation route to the final products. © 2013 American Chemical Society

Chiral thiophosphorylated thioureas: Synthesis, structure, and cyclization reaction

© 2014 Wiley Periodicals, Inc. A number of chiral racemic and enanthiopure thiophosphorylated thioureas were synthesized by the reaction of 2-aminobutan-1-ol and 1-(a-aminobenzyl)-2-naphthol with O,O-diethyl thiophosphoryl isothiocyanate. It was found that such thioureas undergo the cyclization reaction under basic conditions with hydrogen sulfide elimination and the formation of thiophosphorylated oxasines. XRay single crystal diffraction revealed that the structure of thiourea is close to the prereaction state of the cyclization reaction

Chiral thiophosphorylated thioureas: Synthesis, structure, and cyclization reaction

© 2014 Wiley Periodicals, Inc. A number of chiral racemic and enanthiopure thiophosphorylated thioureas were synthesized by the reaction of 2-aminobutan-1-ol and 1-(a-aminobenzyl)-2-naphthol with O,O-diethyl thiophosphoryl isothiocyanate. It was found that such thioureas undergo the cyclization reaction under basic conditions with hydrogen sulfide elimination and the formation of thiophosphorylated oxasines. XRay single crystal diffraction revealed that the structure of thiourea is close to the prereaction state of the cyclization reaction

Chiral thiophosphorylated thioureas: Synthesis, structure, and cyclization reaction

© 2014 Wiley Periodicals, Inc. A number of chiral racemic and enanthiopure thiophosphorylated thioureas were synthesized by the reaction of 2-aminobutan-1-ol and 1-(a-aminobenzyl)-2-naphthol with O,O-diethyl thiophosphoryl isothiocyanate. It was found that such thioureas undergo the cyclization reaction under basic conditions with hydrogen sulfide elimination and the formation of thiophosphorylated oxasines. XRay single crystal diffraction revealed that the structure of thiourea is close to the prereaction state of the cyclization reaction