Browsing by Subject "Insertion reactions"

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    Insertion Reactions of Isocyanides into the Metal-C(sp3) Bonds of Ylide Complexes
    (Elsevier, 2019-08-30) Chicote Olalla, María Teresa; Saura-Llamas, Isabel; García-Yuste, María Francisca; Bautista, Delia; Vicente, José; Química Inorgánica
    The synthesis of the previously reported complexes [Pd(C,C-CHCO2R)2PPh2}(mu-Cl)]2 (R = Me (1), Et (2)) has been considerably improved by reacting the phosphonium salts [Ph2P(CH2CO2R)2]Cl with Pd(OAc)2. Complexes 1 and 2 react with isocyanides R'NC (R' = C6H4Me2-2,6 (Xy), C6H4I-2 and tBu) to give complexes of the type [Pd{C,C-{C(CO2R)=C(NHR')}(CHCO2R)PPh2}Cl(CNR')], resulting from the insertion of the unsaturated molecule in one of their Pd-C bonds and the hydrogen transfer from the methine CH to the iminobenzoyl nitrogen. These are the first insertion reactions observed in the Pd-C bond of a P-ylide complex. The crystal structure of the complex [Pd{C,C-{C(CO2Me)=C(NHXy)}(CHCO2Me)PPh2}Cl(CNXy)] (3) is reported.
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    Palladium-Mediated Functionalization of Benzofuran and Benzothiophene Cores
    (ACS, 2018-12-24) Pérez-Gómez, Marta; Hernández-Ponte, Sergio; García-López, José Antonio; Frutos-Pedreño, Roberto; Bautista, Delia; Saura-Llamas, Isabel; Vicente, José; Química Inorgánica
    The palladation reactions of 2-heteroaromatic primary phenethylamines bearing a benzofuran and benzothiophene nuclei have been studied. We have assessed the reactivity of the corresponding dimeric six-membered palladacycles (arising from C-H metalation) toward neutral ligands and unsaturated species. The insertion reactions of isocyanides into the Pd-C bond of the aforementioned palladacycles allowed the isolation of the corresponding iminoacyl intermediates, which could later be decomposed to give the amidine derivatives containing these relevant heterocyclic cores. In contrast, the carbonylation and alkenylation reactions led to straightforward formation of lactams and alkenylated organic derivatives. Interestingly, an unusual hydrogen-bond-promoted E-to-Z isomerization equilibrium of the resulting olefins was observed. Furthermore, we have studied the conditions to perform the alkenylation of the N-Boc derivatives of these substrates in a catalytic fashion. All the organometallic complexes (arising from the C-H activation of the heteroaromatic cores and insertion of isocyanides) and organic products (arising form the decomposition reactions) have been fully characterized, including the X-ray crystal structures of several organometallic and organic derivatives.