Hydrosilylation of aromatic nitriles promoted by solvated rhodium atom-derived catalysts

Caporusso, Anna Maria; Panziera, Nicoletta; Pertici, Paolo; Pitzalis, Emanuela; Salvadori, Piero; Vitulli, Giovanni; Martra, Gianmario

doi:10.1016/s1381-1169(99)00225-3

Cited by 59 publications

(23 citation statements)

References 15 publications

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“…[27,28,41] Very low TONs were observed for both catalysts when the reactions were carried out under one atmosphere pressure of carbon monoxide (Table 1, entries 1Ϫ2), while improved reaction rates resulted on increasing P CO to 10 bar (Table1, entries 3Ϫ8). When the reaction was performed under 10 bar of CO and in the presence of 1 mol% of Rh/mesitylene cocondensate with respect to the silane (Table 1, entry 4), a strong reduction in chemoselectivity was observed, large quantities (43%) of hydrosilylation by-products 12a being formed, together with the desired aldehyde 11a.…”

Section: Silylformylation Of 1-hexynementioning

confidence: 99%

“…Recently we found that homogeneous and heterogeneous catalysts derived from solvated metal atoms (Rh, Pt), generated by the reaction between metal vapours and weakly stabilising organic ligands (metal vapours synthesis technique, [26] MVS), are very efficient for promotion of many different synthetic transformations such as the hydrosilylation of acetylenes [27] and nitriles. [28] For this paper the catalytic activity of mesitylene-solvated Rh atoms in the silylformylation process of acetylenes was investigated. The influence of the substrates' steric hindrance on the regio-and chemoselectivity of the silylformylation reaction was studied extensively, using several substituted alkynes.…”

Section: Introductionmentioning

confidence: 99%

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Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

Aronica¹,

Terreni²,

Caporusso³

et al. 2001

Eur. J. Org. Chem.

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Solvated rhodium atoms, prepared by the metal vapour synthesis technique, promote the silylformylation reaction of variously substituted alkynes R 1 R 2 CH(CH 2 ) n CϵCH, with catalytic activities comparable with and even higher than more common species such as Rh 4 (CO) 12 . Z-Silylalkenals are exclusively formed in high yields (60−95%) indicating syn addition both of CO and of the silane (Me 2 PhSiH) to the triple bond. The chemoselectivity of the process (silylformylation vs. hydrosilylation) is highly affected by the amount of cata-

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Section: Silylformylation Of 1-hexynementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

Aronica¹,

Terreni²,

Caporusso³

et al. 2001

Eur. J. Org. Chem.

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“…One of the important trends in the development of the hydrosilylation reaction has been the synthesis of heterogeneous catalysts for this reaction (6)(7)(8)(9). On the other hand, immobilized complexes or anchored-metal complexes, in which the metal atom is bonded to a polymer support that plays the role of a macroligand, have been used.…”

Section: Introductionmentioning

confidence: 99%

“…For example, Ru-MgO has been used in the benzene hydrogenation reaction (27) and in the hydrogenolysis of cyclopentene (28). Caporusso et al (7) reported a detailed investigation of the hydrosilylation of aromatic nitriles promoted by unsupported-and supportedrhodium metal nanoparticles. They were prepared from arene-solvated rhodium atoms and are excellent catalysts for the selective hydrosilylation of aromatic nitriles.…”

Section: Introductionmentioning

confidence: 99%

The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

González-Jiménez¹,

Martínez-Rosales²,

Cervantes³

2003

Can. J. Chem.

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Heterogeneous platinum catalysts (Pt/SiO 2 ) obtained by the sol-gel process at pH 3 and 9 have been used in the hydrosilylation reaction of 1-alkynes using various silanes. Once the catalysts were activated they were used in the hydrosilylation of 1-alkynes after a short induction period. The product distribution was quite similar in either case but important differences in catalytic activity and turnover reactions were observed. The catalyst obtained in the basic medium after each reaction lost its catalytic activity, so further activation was needed. To understand this behavior, the catalysts were characterized by 29 Si CPMAS NMR, FT IR, and BET surface area measurements. The 29 Si CPMAS NMR studies showed the presence of terminal and bridged hydroxyl groups in the Pt/SiO 2 catalyst at pH = 9. Similar results were observed by FT IR analysis because of the catalysts' synthetic conditions. Résumé : On a utilisé des catalyseurs homogènes de platine (Pt/SiO 2 ) obtenus par le procédé sol-gel à des pH de 3 et de 9 pour effectuer l'hydrosilylation d'alc-1-ynes à l'aide de divers silanes. Une fois les catalyseurs activés, ils étaient utilisés pour effectuer l'hydrosilylation des alc-1-ynes après une courte période d'induction. La distribution des produits est très semblable dans les deux cas, mais on a observé des différences importantes dans l'activité catalytique et dans les réactions de changement. Le catalyseur obtenu en milieu basique perd son activité après chaque réaction et on doit donc procéder à chaque fois à une nouvelle activation. Dans le but de comprendre ce comportement, on a procédé à une caractérisation des catalyseurs par RMN « CPMAS » du 29 Si, par spectroscopie IR à transformée de Fourrier et par des mesures « BET » de l'aire de la surface. Les études de RMN CPMAS du 29 Si ont montré que la présence de groupes hydroxyles pontés et terminaux est minimale dans le catalyseur de Pt/SiO 2 obtenu à un pH de 9. Des résultats semblables ont été obtenus par l'analyse du spectre IR à transformée de Fourier en raison des conditions de synthèse du catalyseur.

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“…of trimethylsilane at 100 °C for 15 h, aromatic nitriles were reduced to the corresponding disilylated amine derivatives in 65-95% yields, showing the functional group tolerance with ester. 100 With homobimetallic rhodium NHC complex C44, nitrile compounds can be also hydrosilylated at 100 °C for 4-6 h leading the corresponding disilylated amine in moderate yields (42-77%). 101 (Figure 4) …”

Section: Scheme 50 Cobalt-catalysed Hydrosilylation Of Nitrilesmentioning

confidence: 99%

Amine synthesis via transition metal homogeneous catalysed hydrosilylation

2016

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International audienceAmines are among the most important compounds due to their wide applications in several areas of importance. Among the numerous synthetic methodologies, this review provides a comprehensive summary of the preparation of amines involving homogeneous transition metal catalysed hydrosilylation methodologies including the reduction of imine, amide, nitro and nitrile derivatives. In addition, challenging tandem reactions such as reductive amination or the use of CO2 as a C-1-building block in N-methylation of amines will also be discussed

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Hydrosilylation of aromatic nitriles promoted by solvated rhodium atom-derived catalysts

Cited by 59 publications

References 15 publications

Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

Amine synthesis via transition metal homogeneous catalysed hydrosilylation

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Hydrosilylation of aromatic nitriles promoted by solvated rhodium atom-derived catalysts

Cited by 59 publications

References 15 publications

Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

The activity of Pt/SiO2 catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

Amine synthesis via transition metal homogeneous catalysed hydrosilylation

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The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes