115464-59-0Relevant articles and documents
Concerning synthesis of ring-A fluorinated anthracyclines. The dioxirane shunt
D'Accolti, Lucia,Fusco, Caterina,Rella, M. Rosaria,Curci, Ruggero
, p. 3009 - 3016 (2003)
In a key step of the synthesis of 8-fluoro anthracycline aglycones such as 7, epoxidation of the electron-poor C8-C9 double bond moiety presented by the 8-acetyl-6,11-dimethoxy-7,10-dihydronaphthacene-5,12-dione starting material can be achieved in high yield and ease of operations using methyl(trifluoromethyl)dioxirane (1b).
Direct synthesis of 3-aryl-1,2,4,5-tetrazine N-1-oxides by the oxidation with methyl(trifluoromethyl)dioxirane
Adam, Waldemar,Van Barneveld, Claus,Golsch, Dieter
, p. 2377 - 2384 (1996)
1,2,4,5-Tetrazines are oxidized by methyl(trifluoromethyl)dioxirane (TFD) to their hitherto unknown N-oxides in excellent yields. A detailed NMR study (1H, 13C, 15N) shows that the N-1 atom of 3-aryl-1,2,4,5-tetrazines 1 is oxidized regioselectively. A Hammett plot (r2 = 0.970) affords a ρ value of -1.53. The correlation of the logarithm of the reaction rates versus the ionization potentials, which were calculated by AM1, is much worse for ionization out of the aromatic system (IP(π); r2 = 0.804) than for ionization out of the higher-energy nitrogen lone pairs (IP(N:); r2 = 0.940). This implies that an electron transfer mechanism is unlikely and an S(N)2 attack by the nitrogen lone pair of the tetrazine on the dioxirane peroxide bond appears to operate.
Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives
Martin, Teo,Galeotti, Marco,Salamone, Michela,Liu, Fengjiao,Yu, Yanmin,Duan, Meng,Houk,Bietti, Massimo
supporting information, p. 9925 - 9937 (2021/06/30)
A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.
A six-step total synthesis of α-thujone and: D 6-α-thujone, enabling facile access to isotopically labelled metabolites
Thamm, Irene,Richers, Johannes,Rychlik, Michael,Tiefenbacher, Konrad
supporting information, p. 11701 - 11703 (2016/10/04)
The short synthesis of α-thujone relies on the functionalization of the readily available dimethylfulvene. Furthermore, the three main metabolites of the natural product were also synthesized. Since d6-acetone can be used as a starting material, the route developed allows for the facile incorporation of isotopic labels which are required for detecting and quantifying trace amounts via GC/MS analysis.