1273-82-1Relevant articles and documents
Slocum et al.
, p. 4429 (1971)
Synthesis and conformational study of bioconjugates derived from 1-acetyl-1′-aminoferrocene and α-amino acids
Semen?i?, Mojca ?aki?,Kova?, Veronika,Kodrin, Ivan,Bari?i?, Lidija,Rapi?, Vladimir
, p. 112 - 123 (2015)
1,1′-Disubstituted ferrocene conjugates present useful and efficient bioorganometallic constraint design to reduce the conformational flexibility of small peptides. In this study we present the first systematic conformational analysis of nonsymmetric ferrocene peptidomimetics (Boc-AA-NH-Fn-COMe; Boc = tert-butoxycarbonyl; AA = Gly, L-Ala, L-Val; Fn = 1,1′-ferrocenylene) and their monosubstituted analogues (Boc-AA-NH-Fc; Fc = ferrocenyl; AA = Gly, L-Ala, L-Val). The spectroscopic data (IR, NMR and CD) were corroborated by DFT calculations and indicated the engagement of the NH group closest to the ferrocene unit in intrachain hydrogen bonds. This medium-strength bond is not disrupted by the introduction of a hydrogen-bonding acceptor on the other ferrocene ring, but rather is accompanied by an additional interchain hydrogen bond, which causes the restricted rotation of ferrocene rings and gives rise to a chiral arrangement of the ferrocene core in a P helical manner.
Main chain ferrocenyl amides from 1-aminoferrocene-1′-carboxylic acid
Heinze, Katja,Schlenker, Manuela
, p. 2974 - 2988 (2004)
The non-natural amino acid 1-aminoferrocene-1′-carboxylic acid is synthesised from ferrocene in eight steps. The folding and association phenomena of amido-substituted ferrocenes in the crystal as well as in solution are studied by X-ray crystallography, IR and NMR spectroscopy and DFT calculations. The amino acid is selectively protected at the amino group with the use of the fluorenyl-9-methoxycarbonyl (Fmoc) group. An amide-linked ferrocene dimer is prepared using the HOBt/DCC protocol for amide formation. In the crystal the dimer forms a hydrogen-bonded sheet structure, while in solution dynamic intramolecular hydrogen bonds are observed by VT 1H NMR and IR spectroscopy. The dynamic flipping process has been rationalised by DFT calculations. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Ratiometric electrochemical detection of Pd???π interactions: application towards electrochemical molecular logic gates
Goggins, Sean,Stark, Oliver P.,Naz, Christophe,Marsh, Barrie J.,Frost, Christopher G.
, p. 749 - 757 (2017)
The widespread and large scale use of platinum group metals, especially palladium, in a wide variety of industrial applications has seen their levels in wastewater streams, roadside dust and even pharmaceuticals significantly rise over recent years. Due to the possible environmental damage and potential health risk this may cause, there is now substantial demand for inexpensive, efficient and robust methods for the detection of palladium. Based upon self-immolative linker technologies, we have designed and synthesised a number of allyl ether-functionalised electrochemical probes to determine the optimum probe structure required to deliver a ratiometric electrochemical detection method capable of achieving a limit of detection of?a proof-of-principle ratiometric electrochemical molecular logic gate.
Schloegl,Mechtler
, p. 150,165 (1966)
Acton,Silverstein
, p. 1487 (1959)
N-ferrocenyl-substituted planar-chiral N-heterocyclic carbenes and their PdII complexes
Bertogg, Andreas,Camponovo, Francesco,Togni, Antonio
, p. 347 - 356 (2005)
The N-ferrocenyl-linked N-heterocyclic carbenes 1a and 1b were obtained by treatment of their imidazolium salts 12a and 12b with potassium tert-butoxide. The latter were shown to be accessible from (R)-1-amino-2-methylferrocene (9) and aminoferrocene, respectively, which were converted into the corresponding formamidines and then subjected to a novel cyclization procedure. Treating the ligand precursors 12a and 12b with [Pd(OAc)2]3 under different reaction conditions afforded the trans-pyridine-substituted Pd II complexes 14a and 14b as well as their trans-triphenylphosphane- substituted counterparts 16a and 16b and, in the case of the chiral ligand precursor, the dinuclear PdII complex 15a. Conformational analysis of the ligands based on the X-ray structures of 12a, 12b and 16a revealed the dependence of the two torsion angles between the central imidazolium core and the adjacent ferrocenyl substituents on the steric and electronic properties of the observed systems. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Catalytically Generated Ferrocene-Containing Guanidines as Efficient Precursors for New Redox-Active Heterometallic Platinum(II) Complexes with Anticancer Activity
Nieto, Daniel,Bru?a, Sonia,González-Vadillo, Ana Ma,Perles, Josefina,Carrillo-Hermosilla, Fernando,Anti?olo, Antonio,Padrón, José M.,Plata, Gabriela B.,Cuadrado, Isabel
, p. 5407 - 5417 (2015)
The potential of structurally new ferrocene-functionalized guanidines as redox-active precursors for the synthesis of heterometallic platinum(II)-guanidine complexes with anticancer activity was studied. To this end, an atom-economical catalytic approach was followed by using ZnEt2 to catalyze the addition of aminoferrocene and 4-ferrocenylaniline to N,N′-diisopropylcarbodiimide. Furthermore, reaction of a platinum(II) source with the newly obtained guanidines Fc-Ni=C(NHiPr)2 (3) and Fc(1,4-C6H4)-N=C(NHiPr)2 (4) provided access to the heterometallic complexes [PtCl2{Fc-N=C(NHiPr)2}(DMSO)] (5), [PtCl2{Fc(1,4-C6H4)-N=C(NHiPr)2}(DMSO)] (6), and [PtCl2{Fc(1,4-C6H4)-N=C(NHiPr)2}2] (7). Electrochemical studies evidence the remarkable electronic effect played by the direct attachment of the guanidine group to the ferrocene moiety in 3, making its one-electron oxidation extremely easy. Guanidine-based Fe-Pt complexes 5 and 6 are active against all human cancer cell lines tested, with GI50 values in the range 1.4-2.6 μM, and are more cytotoxic than cisplatin in the resistant T-47D and WiDr cell lines.
Ratiometric electrochemical detection of alkaline phosphatase
Goggins, Sean,Naz, Christophe,Marsh, Barrie J.,Frost, Christopher G.
, p. 561 - 564 (2015)
A novel ferrocene-derived substrate for the ratiometric electrochemical detection of alkaline phosphatase (ALP) was designed and synthesised. It was demonstrated to be an excellent electrochemical substrate for the ALP-labelled enzyme-linked immunosorbent assay (ELISA). This journal is
Scalable Synthesis of Functionalized Ferrocenyl Azides and Amines Enabled by Flow Chemistry
Boeser, Lisa,Christmann, Mathias,Hartmayer, Bence,Heretsch, Philipp,Kleoff, Merlin,Sarkar, Biprajit,Schwan, Johannes
supporting information, (2020/02/04)
A scalable access to functionalized ferrocenyl azides has been realized in flow. By halogen-lithium exchange of ferrocenyl halides and trapping with tosyl azide, a variety of functionalized ferrocenyl azides were obtained in high yields. To allow a scalable preparation of these potentially explosive compounds, a flow protocol was developed accelerating the reaction time to minutes and circumventing accumulation of potentially hazardous intermediates. The corresponding ferrocenyl amines were then prepared by a reliable reduction process.
Enantioselective Twofold C?H Annulation of Formamides and Alkynes without Built-in Chelating Groups
Chen, Hao,Luan, Yu-Xin,Wang, Yin-Xia,Ye, Mengchun
supporting information, p. 9428 - 9432 (2020/04/17)
Twofold C?H annulation of readily available formamides and alkynes without built-in chelating groups was achieved. Ni?Al bimetallic catalysis enabled by a bulky BINOL-derived chiral secondary phosphine oxide (SPO) ligand proved to be critical for high reactivity and high selectivity. This reaction uses readily available formamides as starting materials and provides a concise synthetic pathway to a broad range of chiral ferrocenes in 40–98 % yield and 93–99 % ee.
