Reactions of 1-Arylbenziodoxolones with Azide Anion: Experimental and Computational Study of Substituent Effects
New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It was found that independent of the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho position of the aryl ring slows the reaction down, while the presence of a moderately electron-withdrawing bromine substituent in para position to the iodine atom in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para position to the iodine atom in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.
Yusubov, Mekhman S.,Soldatova, Natalia S.,Postnikov, Pavel S.,Valiev, Rashid R.,Svitich, Dmitry Y.,Yusubova, Roza Y.,Yoshimura, Akira,Wirth, Thomas,Zhdankin, Viktor V.
Synthesis of arylbenziodoxoles using pseudocyclic benziodoxole triflate and arenes
An acid activated pseudocyclic hypervalent iodine reagent, 2-[hydroxy(trifluoromethanesufonyloxy)]-iodobenzoic acid, can easily react with various arenes in the presence of trifluoromethanesulfonic acid to produce pseudocyclic diaryliodonium triflate salt
Yoshimura, Akira,Larson, Scott M.,Frahm, Gunnar B.,Huss, Christopher D.,Rohde, Gregory T.,Nemykin, Victor N.,Yusubov, Mekhman S.,Saito, Akio,Zhdankin, Viktor V.
p. 35 - 49
(2020/10/30)
Thermal stability of N-heterocycle-stabilized iodanes-A systematic investigation
The thermal stability of pseudocyclic and cyclic N-heterocycle-stabilized (hydroxy)aryl-and mesityl(aryl)-λ3-iodanes (NHIs) through thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) is investigated. Peak decomposition temperatures (Tpeak) were observed within a wide range between 120 and 270 °C. Decomposition enthalpies (ΔHdec) varied from-29.81 to 141.13 kJ/mol. A direct comparison between pseudocyclic and cyclic NHIs revealed high Tpeak but also higher ΔHdec values for the latter ones. NHIs bearing N-heterocycles with a high N/C-ratio such as triazoles show among the lowest Tpeak and the highest ΔHdec values. A comparison of NHIs with known (pseudo)cyclic benziodoxolones is made and we further correlated their thermal stability with reactivity in a model oxygenation.
Boelke, Andreas,Vlasenko, Yulia A.,Yusubov, Mekhman S.,Nachtsheim, Boris J.,Postnikov, Pavel S.
p. 2311 - 2318
(2019/10/16)
Preparation and X-ray structural study of 1-arylbenziodoxolones
Various 1-arylbenziodoxolones can be conveniently prepared from 2-iodobenzoic acid and arenes by a one-pot procedure using Oxone (2KHSO 5·KHSO4·K2SO4) as an inexpensive and environmentally safe oxidant. This procedure is also applicable for the synthesis of the 7-methylbenziodoxolone ring system using 2-iodo-3-methylbenzoic acid as starting compound. Structures of four 1-arylbenziodoxolone derivatives were established by single-crystal X-ray diffraction analysis. An enhanced reactivity of 1-aryl-7-methylbenziodoxolones toward nucleophiles compared to unsubstituted 1-arylbenziodoxolones has been found.
Yusubov, Mekhman S.,Yusubova, Roza Y.,Nemykin, Victor N.,Zhdankin, Viktor V.
p. 3767 - 3773
(2013/06/05)
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