Synthesis of 1-ferrocenyl-2-aryl(heteroaryl)acetylenes and 2-ferrocenylindole derivatives via the Sonogashira–Heck–Cassar reaction

Torres, Javier Rodríguez; Pilli, Ronaldo A.; Vargas, Maria D.; Violante, Flávio A.; Garden, Simon J.; Pinto, Ângelo C.

doi:10.1016/s0040-4020(02)00394-0

Cited by 58 publications

(32 citation statements)

References 72 publications

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Section: Introductionmentioning

confidence: 99%

“…Addition, alkylation, acylation, condensation-dehydration, coupling and nucleophilic substitution reactions have been employed to link this group to a variety of compounds. [2][3][4]6,7 The mechanisms of the cytotoxicity of ferrocene derivatives have been investigated.8 Osella et al 9 proposed that the cytotoxic activity of ferrocenium salts is due to their ability to generate oxygen active species that induce oxidative DNA damage. Kondapi et al 10,11 have shown that ferrocene derivatives inhibit topoisomerase II, a major molecular target for a number of DNA-binding anticancer drugs.…”

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confidence: 99%

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Synthesis of ferrocenyl oxindole compounds with potential anticancer activity

Silva¹,

Ribeiro²,

Pinto³

et al. 2008

J. Braz. Chem. Soc.

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Compostos oxindol-ferrocenos com potencial atividade anticâncer foram preparados a partir de reações de oxindóis substituídos e carboxaldeído-ferroceno na presença de KOH como catalisador. Os produtos foram caracterizados por dados espectroscópicos incluindo RMN de 1 H e 13 C, infravermelho e espectrometria de massas. As configurações E e Z foram estabelecidas por experimentos de nOe ou NOESY.A series of ferrocenyl oxindoles with potential anticancer activity were prepared from the reactions of substituted oxindoles and ferrocenylcarboxyaldehyde in the presence of KOH as catalyst. The products were characterized by spectral data including 1 H and 13 C NMR, IR and mass spectrometry. The E and Z configurations were established by nOe or NOESY experiments. Keywords: ferrocenyl oxindoles, oxindoles, ferrocenecarboxyaldehyde IntroductionThe ferrocenyl (Fc) group has been incorporated to the structure of a number of biologically active molecules resulting in increased anticancer 1,2 and antimalarial [3][4][5] activity, amongst others. Addition, alkylation, acylation, condensation-dehydration, coupling and nucleophilic substitution reactions have been employed to link this group to a variety of compounds. [2][3][4]6,7 The mechanisms of the cytotoxicity of ferrocene derivatives have been investigated.8 Osella et al. 9 proposed that the cytotoxic activity of ferrocenium salts is due to their ability to generate oxygen active species that induce oxidative DNA damage. Kondapi et al. 10,11 have shown that ferrocene derivatives inhibit topoisomerase II, a major molecular target for a number of DNA-binding anticancer drugs.Indolin-2-ones have been shown to exhibit antitumor activity by inhibiting receptor tyrosine kinases VEGF-R, PDGF-R or CDK.12 The indolin-2-one 1 (sunitinib) has been approved by the U.S. We describe herein the condensation reactions of several oxindole derivatives with FcC(O)H in the presence of KOH in EtOH from which good to excellent yields of the products with E and Z configurations were obtained (Scheme 1). 16The products were characterized by mass spectrometry and infrared, 1 H and 13 C NMR spectroscopies, including nOe and NOESY experiments for the determination of the double-bond geometry. 1245 Vol. 19, No. 7, 2008 Preliminary studies of the reaction of oxindole with FcC(O)H (Table 1) were carried out to assess the catalytic potential of various bases. Except for Et 3 N, all the bases employed led to good conversions. However, formation of products with both E and Z configurations depend on the base employed. The use of KOH in EtOH gave the best yield and selectivity for the E-isomer 2a (entry 1). In the presence of piperidine (entry 3) we were able to isolate the E-isomer 2a in 67% yield together with a 30% isolated yield for the corresponding Z-isomer 2b. The geometries of isomers 2a and 2b were determined by nOe experiments and NOESY interactions. The NOESY experiment for 2a shows a correlation between H4 and H2' of the cyclopentadienyl ring, thus revealing an (E)-configuration for this isom...

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Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis of ferrocenyl oxindole compounds with potential anticancer activity

Silva¹,

Ribeiro²,

Pinto³

et al. 2008

J. Braz. Chem. Soc.

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“…Co-ordination of 1 9 and of the alkynes PhCCC 6 H 4 -4-R (R = NO 2 and CN) 10 to [Ru 3 (CO) 12 ] to produce [Ru 3 (µ 3 -η 2 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) and the analogous clusters 4 and 5, respectively, (see Scheme) was carried out as described previously for other RCCR' (R =R' = H, Ph (3), Me and R = H, R' =Ph). P NMR spectra of the unsymmetrical derivatives 2 and 4-5 the dppm phosphorus nuclei appear as two doublets (J P-P 130Hz) whose chemical shift difference decreases with the decreasing electronic asymmetry of the co-ordinated alkyne (2>5>4).…”

Section: Resultsmentioning

confidence: 99%

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Rosseto¹,

Torres²,

Stein³

et al. 2003

J. Braz. Chem. Soc.

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A coordenação de FcCCC 6 H 4 -4-NO 2 (1) a uma carbonila polinucleada (cluster) de rutênio resultou na formação de [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2). Os voltamogramas cíclicos destes compostos e dos clusters análogos [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) permitiram avaliar as comunicações eletrônicas entre os diferentes sítios de oxi-redução (grupos ferrocenil e -NO 2 e o fragmento Ru 3 ) e analisar as capacidades relativas doadora-receptora de cada um dos três centros de oxi-redução que compõem 2. Além disto, a inércia de 2, em comparação com os clusters 3-5, os quais sofrem fácil perda de CO, foi atribuída à interação entre o grupo ferrocenil e a base metálica.The co-ordination of FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to yield [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) is reported. The cyclic voltammograms of these compounds and of the analogous clusters [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) allowed an evaluation of the electronic communications between the different redox sites (ferrocenyl and -NO 2 groups, and Ru 3 moiety) and an analysis of the relative electron donor-acceptor capabilities of each of the three redox centres that compose 2. Furthermore, the inertness of 2, compared with clusters 3-5 which loose CO readily was attributed to the interaction between the ferrocenyl group and the metallic frame.Keywords: ruthenium cluster, ferrocene, alkyne, cyclic voltammetry IntroductionStudies of electronic interactions in systems containing multiple redox-active centres are of fundamental importance in the development of molecular-based electronic devices.1 Alkynes can be an elegant option in the search of systems containing multi-redox sites, once they can serve as conjugated bridges between groups of different electronic densities.2 In addition, they are remarkably versatile in their co-ordinating abilities to different metals (σ or π-fashion), that can result in the generation of novel mono or polynuclear metal complexes with attractive properties.3 Compounds derived from ferrocene have been extensively investigated for materials science 4 due to their low cost, stability and interesting redox properties, and can be used in molecular ferromagnets, molecular sensors, electrochemical agents, liquid crystals and non-linear optical materials. 5The aim of this work was to combine the electronic properties of alkynes, the ferrocenyl fragment and carbonyl clusters to build a new supramolecular compound containing various redox sites. Co-ordination of the ferrocenylalkyne FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to produce [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) was therefore investigated. In cluster 2, the ferrocenyl fragment can act as an electron donor in charge-transfer processes, 6 the -NO 2 group as an electron acceptor 7 and the ruthenium moiety as a reservoir of electrons, depending on the co-ordinated ligands...

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“…In recent years, the design of new ferrocene derivatives has been of considerable interest, because of their utility in organic synthesis [1], catalysis [2], materials science [3,5], asymmetric synthesis [6], medicinal chemistry [7][8] and electrochemistry [9][10][11][12]. Our interests in ferrocene derivatives containing (methylamino)benzonitrile and N-methylnitroaniline groups arises from the fact that similar compounds such as N-(ferrocenylmethyl)benzene-carboxamide derivatives possess broad range of biological activities [13].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Electrochemical Properties of N-(Ferrocenylmethyl)Aminobenzonitrile and N-(Ferrocenylmethyl)Nitroaniline Derivatives

Boubekri

Khelef

Terki

et al. 2015

ILCPA

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Seven novel ferrocene derivatives containing (methylamino)benzonitrile and Nmethylnitroaniline groups (3a-3f and 4) have been synthesized by conventional methods and characterized by FT-IR, NMR and cyclic voltammetry. The electrochemical behavior of these compounds (3a-3f) has been studied by cyclic voltammetry measurements at a platinum electrode in acetonitrile/0.1 M TBAP. The ferrocenyl group in all compounds showed similar reversible oneelectron redox process, suggesting that the ferrocene moieties are equivalent and that there are no interactions among them. The formal potential, , is shifted to the more positive potential, indicating that the (methylamino)benzonitrile and N-methylnitroaniline introduced to ferrocene moiety exercise an electron-withdrawing effect.

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Synthesis of 1-ferrocenyl-2-aryl(heteroaryl)acetylenes and 2-ferrocenylindole derivatives via the Sonogashira–Heck–Cassar reaction

Cited by 58 publications

References 72 publications

Synthesis of ferrocenyl oxindole compounds with potential anticancer activity

Synthesis of ferrocenyl oxindole compounds with potential anticancer activity

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Synthesis and Electrochemical Properties of N-(Ferrocenylmethyl)Aminobenzonitrile and N-(Ferrocenylmethyl)Nitroaniline Derivatives

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