1665-64-1Relevant articles and documents
Diastereoselective synthesis of CF3-oxazinoquinolines in water
Muzalevskiy, Vasiliy M.,Belyaeva, Kseniya V.,Trofimov, Boris A.,Nenajdenko, Valentine G.
supporting information, p. 6353 - 6360 (2019/12/03)
A highly efficient stereoselective synthesis of CF3-oxazinoquinolines was elaborated using the reaction of CF3-ynones with quinolines in water. It was demonstrated that under these green conditions, the reaction proceeds up to 20 times faster to provide target compounds in almost quantitative yields. Moreover, this method is devoid of any chromatographic purification to give CF3-oxazinoquinolines with complete diastereoselectivity. The presented eco-friendly approach was found much more efficient than standard reactions in organic solvents. The synthetic utility of the prepared CF3-oxazinoquinolines was demonstrated.
SNAr nucleophilic substitution of 1,9-dihalodipyrrins by S- and N- nucleophiles. Synthesis of new dipyrrins bearing pendant substituents
Leushina, Evgenia,Tikhomirova, Ksenia,Permyakova, Anastasiya,Ilin, Pavel,Terenina, Maria,Anisimov, Alexander,Khoroshutin, Andrey
, p. 149 - 155 (2016/03/19)
5-Aryl-1,9-dichlorodipyrrins react with a series of S- and N- nucleophiles (both alkyl- and aryl- ones). Reagents with mercapto group yield product of double nucleophilic substitution of 5-pheny-1,9-dichlorodipyrrin, i.e. the respective 1,9-bis(alkyl-of arylthio)dipyrrin. On the contrary, 5-(4-nitrophenyl)-1,9-dichlorodipyrrin causes disulfides formation from the S-aliphatic substrates, whereas nucleophilic substitution remains the main path of the reaction for S-aryl ones. The reaction of N-Alkyl nucleophiles proceeds as mono-substitution. UV-Vis spectra feature a batochromic shift for bis-S-substituted products and a hypsochromic shift for mono-N-substituted ones, with respect to the starting dichlrorides.
Unusual multistep reaction of C70Cl10 with thiols producing C70[SR]5H
Khakina, Ekaterina A.,Peregudov, Alexander S.,Yurkova, Anastasiya A.,Piven, Natalya P.,Shestakov, Alexander F.,Troshin, Pavel A.
, p. 1215 - 1219 (2016/03/01)
We report a reaction of the chlorofullerene C70Cl10 with thiols producing C70[SR]5H with all organic addends attached around one central pentagon at the pole of the C70 cage. This reaction was shown to proceed via a complicated radical pathway, presumably involving addition, substitution, rearrangement, and/or elimination steps. The obtained C70[SR]5H products were shown to be very unstable and undergo quantitative decomposition to pristine C70, RSSR, and RSH at elevated temperatures (e.g., 50 °C). Quantum chemical calculations and NMR spectroscopy data showed that cleavage of organic addends from the fullerene cage could be induced by solvation effects in solution.
An insight into the radical thiol/yne coupling: The emergence of arylalkyne-tagged sugars for the direct photoinduced glycosylation of cysteine-containing peptides
Minozzi, Matteo,Monesi, Alessandro,Nanni, Daniele,Spagnolo, Piero,Marchetti, Nicola,Massi, Alessandro
experimental part, p. 450 - 459 (2011/04/19)
An explorative study of the Thiol-Yne Coupling (TYC) reaction has been carried out using an aliphatic (1-octyne) and an aromatic alkyne (phenylacetylene) and two alkanethiols (methyl thioglycolate and N-acetyl-L-cysteine methyl ester). The outcomes of the TYC reactions strongly depend on the experimental conditions (e.g., temperature, solvent, and alkyne/thiol ratio), but these can be properly adjusted to achieve selective production of either mono-or bis-coupling products. With respect to 1-octyne, phenylacetylene undergoes notably easier radical hydrothiolation, further showing a notably higher aptitude for monohydrothiolation exclusive of bis-hydrothiolation. The overall findings were exploited in glycosylation of cysteine derivatives as well as of cysteine-containing peptides. A sugar featuring an arylacetylene moiety gave rise to a true click-reaction, that is, glycosylation of the tripeptide glutathione in its native form, by means of virtually equimolar amounts of reagents. This reaction was successfully applied, under physiological conditions, to a cysteine-containing nonapeptide with marked advantages over the analogous Thiol-Ene Coupling (TEC) derivatization. A TYC/TEC sequence affording bis-armed cysteine derivatives through dual functionalization of an alkynyl sugar was additionally devised.
