- 1,1′-Diacetyloctamethylferrocene: An overlooked and overdue synthon leading to the facile synthesis of an octamethylferrocenophane
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This paper describes the facile preparation of 1,1′-diacetyloctamethylferrocene (2) by acylation of octamethylferrocene (1) with acetyl chloride. Chloroformylation with POCl3/DMF of 2 affords a variety of products, including 1,1′-bis-(1-chlorovinyl)octamethylferrocene (3b) in high yield. Compound 3b cyclises in aqueous sodium hydroxide/DMF to an octamethyl[1,4]-ferrocenophane bearing a 1-dimethylaminobuta-1,3-diene-handle (4).
- Roemer, Max,Skelton, Brian W.,Piggott, Matthew J.,Koutsantonis, George A.
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- Tuning of Oxidation Potential of Ferrocene for Ratiometric Redox Labeling and Coding of Nucleotides and DNA
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Three sets of 7-deazaadenine and cytosine nucleosides and nucleoside triphosphates bearing either unsubstituted ferrocene, octamethylferrocene and ferrocenecarboxamide linked through an alkyne tether to position 7 or 5, respectively, were designed and synthesized. The modified dNFcXTPs were good substrates for KOD XL DNA polymerase in primer extension and were used for enzymatic synthesis of redox-labelled DNA probes. Square-wave voltammetry showed that the octamethylferrocene oxidation potential was shifted to lower values, whilst the ferrocenecarboxamide was shifted to higher potentials, as compared to ferrocene. Tailed PEX products containing different ratios of Fc-labelled A (dAFc) and FcPa-labelled C (dCFcPa) were synthesized and hybridized with capture oligonucleotides immobilized on gold electrodes to study the electrochemistry of the redox-labelled DNA. Clearly distinguishable, fully orthogonal and ratiometric peaks were observed for the dAFc and dCFcPa bases in DNA, demonstrating their potential for use in redox coding of nucleobases and for the direct electrochemical measurement of the relative ratio of nucleobases in an unknown sequence of DNA.
- Fojta, Miroslav,Havran, Luděk,Hocek, Michal,Magri?á, Ivan,O'Sullivan, Ciara K.,Ortiz, Mayreli,Pohl, Radek,Sykorová, Veronika,Simonova, Anna
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supporting information
(2020/01/22)
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- NMR Spectroscopy on Paramagnetic Complexes, XXVII. Paramagnetic 1,1',2,2',3,3',4,4'-Octamethylmetallocenes
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The tetramethylated cyclopentadienyl anion has been prepared from tiglinic acid and reacted with solvated metal(II) chlorides to give new octamethylmetallocenes (Me4cp)2M.For M = V, Cr, Co and Ni the paramagnetic 1H and 13C spectra have been recorded.The NMR data prove the molecular structure and show that all methyl groups rotate almost freely.The methyl proton resonance of the nickelocene may serve as a probe for the adjustment of metallocene properties by ring substitution.Based on qualitative MO arguments the correlation of electron spin densities and paramagnetic shifts lead to an understanding of the signal splitting of cobaltocenes.From the electronic point of view the octamethylmetallocenes may be regarded as being invers to 1,1'-dimethylmetallocenes. - Key words: Octamethylmetallocenes, Paramagnetic 1H/13C NMR
- Koehler, Frank H.,Doll, Karl H.
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p. 144 - 150
(2007/10/02)
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