1271-51-8Relevant articles and documents
Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane
Yu, Songjie,Noble, Adam,Bedford, Robin B.,Aggarwal, Varinder K.
, p. 20325 - 20334 (2019)
[1.1.1]Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and two-electron pathways, hence, providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dimers, and trimers, often with poor selectivity. Herein, we report that nickel(0) catalysis enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of functionalized alkenes to give methylenespiro[2.3]hexane products. Computational studies provide support for initial formation of a Ni(0)-[1.1.1]propellane complex followed by concerted double C-C bond activation to give the key 3-methylenecyclobutylidene-nickel intermediate.
A versatile electrochemical sensing receptor based on a molecularly imprinted polymer
Udomsap, Dutduan,Branger, Catherine,Culioli, Gérald,Dollet, Pascal,Brisset, Hugues
, p. 7488 - 7491 (2014)
Electrochemical molecularly imprinted polymers (e-MIPs) are reported for the first time. Their elaboration is based on the introduction of a redox tracer (vinylferrocene) inside the binding cavities of a cross-linked MIP. Determination of the analyte (benzo[a]pyrene) can be simply performed by measuring the redox tracer signal. the Partner Organisations 2014.
Synthesis and Characterization of a Family of Air-Stable Ferrocene- and Ruthenocene-Containing Primary, Secondary, and Tertiary Phosphines
Kenaree, Amir Rabiee,Cuthbert, Tyler J.,Barbon, Stephanie M.,Boyle, Paul D.,Gillies, Elizabeth R.,Ragogna, Paul J.,Gilroy, Joe B.
, p. 4272 - 4280 (2015)
The synthesis and characterization of a family of air-stable primary, secondary, and tertiary phosphines containing all possible combinations of ethylferrocene and ethylruthenocene substituents are reported. Each phosphine was characterized by 1H, 13C, and 31P NMR spectroscopy, IR and UV-vis absorption spectroscopy, mass spectrometry, and elemental analysis. With the exception of primary ethylruthenocene phosphine 8a, all of the title compounds have been studied by single-crystal X-ray crystallography. Ferrocene-containing phosphines showed maximum absorption at wavelengths of ca. 440 nm and qualitatively reversible oxidation waves in their cyclic voltammograms with intensities scaling to the number of ferrocene units present. The average metal-cyclopentadienyl centroid distances observed for ferrocene-containing phosphines were shorter than those of ruthenocene-containing phosphines, which also had maximum absorption wavelengths of ca. 320 nm and underwent irreversible electrochemical oxidation. Phosphines containing both ethylferrocene and ethylruthenocene substituents displayed properties consistent with the presence of both metallocene types.
Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds
Singh, Jatinder,Ghosh, Sanjib,Deb, Mayukh,Elias, Anil J.
, p. 85 - 91 (2016)
Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.
Synthesis, characterization and second-order nonlinear optical behaviour of ferrocene-diketopyrrolopyrrole dyads: The effect of alkene: Vs. alkyne linkers
Kaur, Sarbjeet,Van Steerteghem, Nick,Kaur, Paramjit,Clays, Koen,Singh, Kamaljit
, p. 9717 - 9726 (2016)
New, thermally stable dipolar ferrocene-diketopyrrolopyrrole (Fc-DPP) dyads with alkene as a linker exhibited structure dependent first hyperpolarizabilities, βHRS, recorded by a femtosecond HRS technique using a femtosecond (120 fs) pulsed laser light system at 900 nm at ambient temperature. On the basis of linear optical, electrochemical and TD-DFT studies, a good structure-polarization relationship has been established to account for the observed trends in first hyperpolarizabilities. The dyads exhibited fluctuating but matching solvatochromism. Nonlinear optical properties are modulated both by the strength of the acceptor as well as the length and nature of the π-conjugation bridge. βHRS of the dyads were compared with structurally related dyads in which the DPP core and the Fc donor are linked via an alkyne bridge. It is interesting to observe that the replacement of an alkyne link with alkene in these D-π-A chromophores does not necessarily furnish enhanced βHRS.
Pd-catalyzed rearrangement of ferrocenylalkyl vinyl ethers to the related aldehydes and ketones
Kolyvanov, Nikita A.,Oparina, Ludmila A.,Tarasova, Olga A.,Albanov, Alexander I.,Gusarova, Nina K.,Trofimov, Boris A.
, (2020)
Ferrocenylalkyl vinyl ethers undergo a facile rearrangement (CH2Cl2, 20–25 °C, 0.5 h) in the presence of 3–4 mol% PdCl2(MeCN)2, to give the corresponding ferrocenyl alkanals or alkanones in high yields. Yttrium and lanthanide triflates and Lewis acids (AlCl3) were less effective as catalysts.
Synthesis, spectra and crystal structure of (E)-(CO)2(NO)Cr[(η5-C5H 4)-CH=CH(η5-C5H4)]Cr(CO) 2(NO)
Wang, Yu-Pin,Lui, Xen-Hum,Lin, Bi-Son,Tang, Wei-Der,Lin, Tso-Shen,Liaw, Jen-Hai,Wang, Yu,Liu, Yi-Hung
, p. 310 - 319 (1999)
Compounds 1,2-bis[(η5-cyclopentadienyl)dicarbonylnitrosylchromium]ethene (7) (hereafter called 1,2-dicynichrodenylethene) and 1,2-diferrocenylethene (10) were prepared from formylcynichrodene (3) and formylferrocene (9), respectively, via the McMurry's low-valent titanium coupling method. Compounds (η5-vinylcyclopentadienyl)dicarbonylnitrosylchromium (6) and vinylferrocene (11) were obtained by the dehydration of the corresponding alcohols. The structure of 7 was solved by an X-ray diffraction study: space group, P21/c; monoclinic; a=6.379(5), b=11.295(3) and c=11.9352(24); Z=2. It turns out that compound 7 adopts a transoid conformation at the ethenylene bridge and the two cyclopentadienyl rings are coplanar. The nitrosyl group in each cynichrodenyl moiety of 7 is located at the side towards the corresponding ethenylene carbon atom with a twist angle of 46.5°. The chemical shifts of H(2)-H(5) protons and C(2)-C(5) carbon atoms of a series of vinyl derivatives of compounds bearing cyclopentadienyl rings have been assigned using two-dimensional HetCOR-NMR spectroscopy. For the derivatives of cynichrodene (1) and ferrocene, it was found that the shielding of C(2,5) and C(3,4) carbon atoms is parallel to the shielding of the ortho- and para-carbon atoms of benzene derivatives. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of 13C-NMR data. Surprisingly, the vinyl group donates electron density to the adjacent cynichrodene moieties rather than withdraws from them.
Dynamic parallel kinetic resolution of α-ferrocenyl cation initiated by chiral Br?nsted acid catalyst
Kikuchi, Jun,Korenaga, Toshinobu,Obayashi, Ren,Terada, Masahiro,Toda, Yasunori
, p. 10306 - 10312 (2021)
The dynamic parallel kinetic resolution (DPKR) of an α-ferrocenyl cation intermediate under the influence of a chiral conjugate base of a chiral phosphoric acid catalyst has been demonstrated in an SN1 type substitution reaction of a racemic ferrocenyl derivative with a nitrogen nucleophile. The present method provides efficient access to a ferrocenylethylamine derivative in a highly enantioselective manner, which is potentially useful as a key precursor of chiral ligands for metal catalysis. The mechanism of the present intriguing resolution system was elucidated by control experiments using the enantio-pure precursor of relevant α-ferrocenyl cation intermediates and the hydroamination of vinylferrocene. Further theoretical studies enabled the elucidation of the origin of the stereochemical outcome as well as the efficient DPKR. The present DPKR, which opens a new frontier for kinetic resolution, involves the racemization process through the formation of vinylferrocene and the chemo-divergent parallel kinetic resolution of the enantiomeric α-ferrocenyl cations generated by the protonation/deprotonation sequence of vinylferrocene.
Synthesis of ferrocenyl-bearing dendrimers with a resorcinarene core
Valderrama, M.I. Reyes,García, R.A. Vázquez,Klimova,Klimova,Ortiz-Frade,García, M. Martínez
, p. 1597 - 1605 (2008)
A series of ferrocenyl ended dendrons containing π-conjugated systems were obtained using Wittig and Heck reactions. The dendrons were attached to eight functionalized resorcinarenes via Williamson reaction obtaining high molecular weight dendrimers. No electronic communication between metal centers was observed by cyclic voltammetry. All the dendrimers were characterized by 1H, 13C NMR, FTIR, UV-Vis, MALDI-TOF, elemental analyses, and electrochemical studies.
First-and second-generation heterometallic dendrimers containing ferrocenyl-ruthenium(II)-arene motifs: Synthesis, structure, electrochemistry, and preliminary cell proliferation studies
Govender, Preshendren,Lemmerhirt, Heidi,Hutton, Alan T.,Therrien, Bruno,Bednarski, Patrick J.,Smith, Gregory S.
, p. 5535 - 5545 (2014)
Four first- and second-generation heterometallic ferrocenyl derived p-cymene-Ru(II) metallodendrimers, of general formula [DAB-PPI{(κ6-p-cymene)Ru((C7H5NO)-2-N,O)PTA(5-ferrocenylvinyl)}n][PF6/su
