372-09-8Relevant articles and documents
Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
Fabre,Reynes
, p. 1360 - 1362 (2010)
The electrocarboxylation of chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co-C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen).
5-Oxyacetic Acid Modification Destabilizes Double Helical Stem Structures and Favors Anionic Watson–Crick like cmo5U-G Base Pairs
Strebitzer, Elisabeth,Rangadurai, Atul,Plangger, Raphael,Kremser, Johannes,Juen, Michael Andreas,Tollinger, Martin,Al-Hashimi, Hashim M.,Kreutz, Christoph
, p. 18903 - 18906 (2018)
Watson–Crick like G-U mismatches with tautomeric Genol or Uenol bases can evade fidelity checkpoints and thereby contribute to translational errors. The 5-oxyacetic acid uridine (cmo5U) modification is a base modification at the wobble position on tRNAs and is presumed to expand the decoding capability of tRNA at this position by forming Watson–Crick like cmo5Uenol-G mismatches. A detailed investigation on the influence of the cmo5U modification on structural and dynamic features of RNA was carried out by using solution NMR spectroscopy and UV melting curve analysis. The introduction of a stable isotope labeled variant of the cmo5U modifier allowed the application of relaxation dispersion NMR to probe the potentially formed Watson–Crick like cmo5Uenol-G base pair. Surprisingly, we find that at neutral pH, the modification promotes transient formation of anionic Watson–Crick like cmo5U?-G, and not enolic base pairs. Our results suggest that recoding is mediated by an anionic Watson–Crick like species, as well as bring an interesting aspect of naturally occurring RNA modifications into focus—the fine tuning of nucleobase properties leading to modulation of the RNA structural landscape by adoption of alternative base pairing patterns.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
Synthesis of α-aminonitriles using aliphatic nitriles, α-amino acids, and hexacyanoferrate as universally applicable non-toxic cyanide sources
Nauth, Alexander M.,Konrad, Tim,Papadopulu, Zaneta,Vierengel, Nina,Lipp, Benjamin,Opatz, Till
supporting information, p. 4217 - 4223 (2018/09/29)
In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxidative C-H functionalization. Mn(OAc)2 was found to catalyze the efficient release of HCN from these cyanohydrins or from acetone cyanohydrin under acidic conditions and, in combination with the two previous transformations, permits the use of protein biomass as a non-toxic source of HCN.