8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Hydroamination: direct addition of amines to alkenes and alkynes.

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Electrophilic Trifluoromethylation by Use of Hypervalent Iodine Reagents

3.10 - Nitroxide-Mediated Polymerization

Kinetics of Living Radical Polymerization

1,3-diphenylisobenzofuran (DPBF) is a fluorescent molecule which possesses a highly specific reactivity towards singlet oxygen (1O2) forming an endoperoxide which decomposes to give 1,2-dibenzoylbenzene. This reaction between DPBF and 1O2 can be followed by measuring the decrease in fluorescence intensity of DPBF. In order to check the specificity of DPBF toward free radicals a series of experiments was carried out in Triton-X micelles and in natural systems (rat liver microsomes), in which DPBF was reacted with hydroxy (HO•), alkyloxy (RO•), alkylperoxy (ROO•), and C-centered radicals (2-cyanoisopropyl radical). In all cases, the DPBF is rapidly transformed to 1,2-dibenzoylbenzene in the case of O-centered radicals and to the corresponding adduct in the case of 2-cyanoisopropyl radical. The experiments in the model systems were also carried out from the chemical point of view and the reaction products were isolated and identified. From the results obtained, it should be stressed that DPBF must be used with caution in complex biological systems for the detection of 1O2, as it also reacts with different radical species.

On the Use of 1,3-Diphenylisobenzofuran (Dpbf). Reactions With Carbon and Oxygen Centered Radicals in Model and Natural Systems

Unexpected deoxygenation of 2,2,6,6-tetramethylpiperidine-1-oxyl (tempo) by thiyl radicals through the formation of arylsulphinyl radicals

Synthesis and thermal stability of alkoxyamines

Chemical and Electrochemical Study on the Interactions of Aminoxyls with Superoxide Anion

Intramolecular aminomercuration of the alkenyl α-amino phosphonate 6 followed by sodium borohydride reduction leads to the diethyl (4-(benzyloxymethyl)-2,5,5-trimethylpyrrolidinyl)-phosphonate 7. Oxidation of the phosphonates 7 and 8 with 3-chloroperbenzoic acid led to the stable 2-phosphonylpyrrolidinyl aminoxyl radicals 9 and 10 bearing a 4-(hydroxymethyl)substituent

Pierluigi Stipa

Papers

On the Use of 1,3-Diphenylisobenzofuran (Dpbf). Reactions With Carbon and Oxygen Centered Radicals in Model and Natural Systems

Unexpected deoxygenation of 2,2,6,6-tetramethylpiperidine-1-oxyl (tempo) by thiyl radicals through the formation of arylsulphinyl radicals

Synthesis and thermal stability of alkoxyamines

Chemical and Electrochemical Study on the Interactions of Aminoxyls with Superoxide Anion

β-Phosphorylated five-membered ring nitroxides: synthesis and ESR study of 2-phosphonyl-4-(hydroxymethyl)pyrrolidine aminoxyl radicals