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Abdol R. Hajipour - One of the best experts on this subject based on the ideXlab platform.

Fatemeh Rafiee - One of the best experts on this subject based on the ideXlab platform.

Jose Vicente - One of the best experts on this subject based on the ideXlab platform.

Delia Bautista - One of the best experts on this subject based on the ideXlab platform.

  • Reactivity toward CO of Eight-Membered Palladacycles Derived from the Insertion of Alkenes into the Pd–C Bond of Cyclopalladated Primary Arylalkylamines of Pharmaceutical Interest. Synthesis of Tetrahydrobenzazocinones, Ortho-Functionalized Phenethyl
    2016
    Co-Authors: José-antonio Garcı́a-lópez, Delia Bautista, María-josé Oliva-madrid, Isabel Saura-llamas, José Vicente
    Abstract:

    The ortho-metalated complex [Pd­{C,N-C6H2CH2CH2NH2-2,(OMe)2-4,5}­(μ-Br)]2 (1a) derived from Homoveratrylamine reacts with ethyl acrylate, methyl vinyl ketone, or 2-norbornene to give the dimeric complex arising from the insertion of the alkene into the Pd–C bond, [Pd­{C,N-CH­(R)­CH2C6H2CH2CH2NH2-2,(OMe)2-4,5}­(μ-Br)]2 (R = CO2Et (2a1), C­(O)­Me (2a2)) or [Pd­{C,N-CH­(C5H8)­CHC6H2CH2CH2NH2-2,(OMe)2-4,5}­(μ-Br)]2 (2a3). Complexes 2a and the phentermine homologues 2b react with CO to afford Pd(0) and (1) tetrahydrobenzazocinones, the heterocycles resulting from CO insertion into the Pd–C bond and C–N coupling, (2) unnatural amino acid derivatives, resulting from CO insertion and the reaction of the obtained acyl complex with the solvent (MeOH), or the product of protonolysis of the Pd–C bond, depending on the nature of the initial cyclopalladated compound, or (3) ureas, alone or mixed with an isocyanate, in the presence of a base. Phentermine derivatives 2b react with HCl to give a dinuclear palladium complex [PdCl­(μ-Cl)­(L)], where L is the amine arising from the protonolysis of the Pd–C bond or the alkyl group resulting from Pd–N bond protonolysis, depending on the nature of the inserted alkene. The crystal structures of some palladium complexes and organic compounds have been determined by X-ray diffraction studies

  • reactivity toward neutral n and p donor ligands of eight membered palladacycles arising from monoinsertion of alkynes into the pd c bond of orthopalladated Homoveratrylamine and phentermine a new example of the transphobia effect
    Organometallics, 2014
    Co-Authors: Mariajose Olivamadrid, Joseantonio Garcialopez, Isabel Saurallamas, Delia Bautista, Jose Vicente
    Abstract:

    Eight-membered palladacycles arising from the insertion of one molecule of alkyne into the Pd–C bond of the palladacycles derived from Homoveratrylamine and phentermine react with neutral N- and P-donor ligands to give mononuclear or unusual dinuclear complexes, containing a vinylarylethylamino bridge, depending on the size of the ligand and the substituents of the palladacycle. Diffusion-ordered nuclear magnetic resonance spectroscopy experiments are used to measure the diffusion coefficients and propose the nuclearity of these complexes in solution. Density functional theory calculations show that steric and electronic (transphobia) effects are responsible for the unprecedented observed reactivity differences. A mechanism for the formation of the unusual dinuclear complexes is proposed.

  • Reactivity of Eight-Membered Palladacycles Arising from Monoinsertion of Alkynes into the Pd–C bond of Ortho-Palladated Phenethylamines toward Unsaturated Molecules. Synthesis of Dihydro-3-Benzazocinones, N7‑amino Acids, N7‑amino Esters, and 3‑Benzaz
    2014
    Co-Authors: María-josé Oliva-madrid, Delia Bautista, José-antonio Garcı́a-lópez, Isabel Saura-llamas, José Vicente
    Abstract:

    From the reactions of isocyanides R3NC with some eight-membered palladacycles arising from the insertion of one molecule of alkyne into the Pd–C bond of the palladacycles derived from Homoveratrylamine and phentermine it is possible to isolate three different types of mononuclear complexes containing (1) coordinated R3NC, (2) coordinated and inserted R3NC, or (3) an unprecedented η3-allyl ligand involving a ketenimine moiety. These complexes decompose under the appropriate conditions to afford metallic palladium and the corresponding eight-membered azacycles arising from C–N coupling processes. The eight-membered palladacycles react with CO in MeOH to yield Pd(0) and amino esters. A singular isomerization process from a fumarate to a maleate was observed and studied by DFT. When the reaction with CO is carried out in the presence of TlTfO, N7-amino acid derivatives can be obtained. This synthetic method can also be used to prepare the N5-amino acids derived from the ortho-metalated Homoveratrylamine or phentermine. Finally, the treatment of one eight-membered palladacycle derived from phentermine with KtBuO in refluxing toluene, followed by addition of HTfO, afforded Pd(0) and a dihydro-3-benzazepinium salt. Crystal structures of every type of compound have been determined by X-ray diffraction studies

  • Reactivity toward Neutral N- and P‑Donor Ligands of Eight-Membered Palladacycles Arising from Monoinsertion of Alkynes into the Pd–C Bond of Orthopalladated Homoveratrylamine and Phentermine. A New Example of the Transphobia Effect
    2014
    Co-Authors: María-josé Oliva-madrid, Delia Bautista, José-antonio Garcı́a-lópez, Isabel Saura-llamas, José Vicente
    Abstract:

    Eight-membered palladacycles arising from the insertion of one molecule of alkyne into the Pd–C bond of the palladacycles derived from Homoveratrylamine and phentermine react with neutral N- and P-donor ligands to give mononuclear or unusual dinuclear complexes, containing a vinylarylethylamino bridge, depending on the size of the ligand and the substituents of the palladacycle. Diffusion-ordered nuclear magnetic resonance spectroscopy experiments are used to measure the diffusion coefficients and propose the nuclearity of these complexes in solution. Density functional theory calculations show that steric and electronic (transphobia) effects are responsible for the unprecedented observed reactivity differences. A mechanism for the formation of the unusual dinuclear complexes is proposed

  • Insertion Reactions on Carbopalladated Benzyne: From Eight- to Nine- and Ten-Membered Palladacycles. Applications to the Synthesis of N‑Heterocycles
    2014
    Co-Authors: María-josé Oliva-madrid, Delia Bautista, José-antonio Garcı́a-lópez, Isabel Saura-llamas, José Vicente
    Abstract:

    The ortho-metalated complexes [Pd­{C,N-C6H2CH2CH2NH2-2,(OMe)2-4,5}­(μ-Br)]2 (A) and [Pd­{C,N-C6H4CH2CMe2NH2-2}­(μ-Cl)]2 (B), derived from Homoveratrylamine and phentermine, respectively, react with benzyne generated in situ, to afford the previously reported eight-membered palladacycles 1a and 1b, respectively, arising from the insertion of one molecule of the aryne into the Pd–Caryl bond. Complexes 1 react with isocyanides RNC (R = Xy, tBu) in 1:4 molar ratio to give the nine-membered iminoacyl palladacycles [Pd­(C,N-C­(NR)-C6H4{C6H2CH2CH2NH2-2­(OMe)2-4,5)-2′})­Br­(CNR)] (R = Xy (2a), R = tBu (3a)) and [Pd­(C,N-C­(NXy)-C6H4{C6H4CH2CMe2NH2-2)-2′})­Cl­(CNR)] (R = Xy (2b), R = tBu (3b)). Complex 2a decomposes in refluxing toluene to afford palladium(0) and 7,8-dihydro-10,11-dimethoxy-5-[(2,6-dimethylphenyl)­imino]­dibenzo­[c,e]­azocinium triflate (4a). When 1b reacts with TlOTf and XyNC (molar ratio 1:2:2), 7,8-dihydro-5-[(2,6-dimethylphenyl)­imino]-7,7-dimethyl­dibenzo­[c,e]­azocinium triflate (4b) is obtained, resulting from an isocyanide insertion/C–N reductive coupling sequence. The amidinium triflates 4a and 4b present E/Z isomerism in CHCl3 solution. The stoichiometric carbonylation of dinuclear complexes 1 renders, after depalladation, the lactams 7,8-dihydro-10,11-dimethoxy­dibenzo­[c,e]­azocin-5­(6H)-one (5a) and 7,8-dihydro-7,7-dimethyl­dibenzo­[c,e]­azocin-5­(6H)-one (5b) or the previously reported ester derivative [2′-MeO2CC6H4C6H2­CH2CH2NH3-2-(OMe)2-4,5]Br (6a) or [2′-MeO2CC6H4C6H4­CH2CMe2NH3-2]Cl (6b), depending on the reaction conditions. The eight-membered palladacycles 1 react with alkenes to afford complexes [PdCl2(biarylamine)2] (7a, 7b, 8b), containing the Heck-type functionalized phenethylamines. The reaction of 1b with tBuOK in toluene at 95 °C, under a N2 atmosphere, affords 6,7-dihydro-6,6-dimethyl-5H-dibenz­[b,d]­azepine (9b), resulting from a C–N reductive coupling process. The crystal structures of compounds [Pd­(C,N-C­(NXy)-C6H4­{C6H2CH2CH2NH2-2­(OMe)2-4,5)-2′})­Br­(CNXy)]·CH2Cl2·1/2H2O (2a·CH2Cl2·1/2H2O), [Pd­(C,N-C­(NXy)-C6H4­{C6H4CH2CMe2NH2-2)-2′})­Cl­(CNXy)]·0.72Et2O·0.28CHCl3 (2b·0.72Et2O·0.28CHCl3), and 7,8-dihydro-10,11-dimethoxy­dibenzo­[c,e]­azocin-5­(6H)-one (5a) have been determined by X-ray diffraction studies

Mariajose Olivamadrid - One of the best experts on this subject based on the ideXlab platform.