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Autoxidation Chemistry: Bridging the Gap Between Homogeneous Radical Chemistry and (Heterogeneous) Catalysis

Hermans, Ive ; Peeters, Jozef ; Jacobs, Pierre

In: Topics in Catalysis, 2008, vol. 48, no. 1-4, p. 41-48

Hydrogen atom transfer (HAT) processes promoted by the quinolinimide-N-oxyl radical: a kinetic and theoretical study

DiLabio, Gino A. ; Franchi, Paola ; Lanzalunga, Osvaldo ; Lapi, Andrea ; Lucarini, Fiorella ; Lucarini, Marco ; Mazzonna, Marco ; Prasad, Viki Kumar ; Ticconi, Barbara

In: The Journal of Organic Chemistry, 2017, vol. 82, no. 12, p. 6133–6141

A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the quinolinimide-N-oxyl radical (QINO) was performed in CH3CN. The HAT rate constants are significantly higher than those observed with the phthalimide- N-oxyl radical (PINO) as a result of enthalpic and polar effects due to the presence of the N-heteroaromatic ring in QINO. The relevance of...

Radicals in stereoselective synthesis and electron transfer reactions

Bernd, Giese ; Sonja, Eckhardt

In: CHIMIA International Journal for Chemistry, 2013, vol. 67, no. 4, p. 200–203

The photocycloaddition of arenes and allenes

Streit, Ursula ; Birbaum, Frédéric ; Quattropani, Anna ; Bochet, Christian G.

In: The Journal of Organic Chemistry, 2013, p. -

In the present work, we report on a new intramolecular para-cycloaddition of arenes with allenes, yielding attractive rigid scaffolds bearing several reactive functionalities to build in further diversity. Bicyclo[2.2.2]octadiene-type products and benzoxepine acetals are formed in this reaction, in ratios and yields depending on the substitution pattern on the aromatic ring, the nature of the...

Experimental and theoretical study of 2,6-difluorophenylnitrene, its radical cation, and their rearrangement products in argon matrices

Carra, Claudio ; Nussbaum, Rafael ; Bally, Thomas

In: ChemPhysChem, 2006, vol. 7(6), p. 1268-1275

2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence of...

Synthesis and application of an electronically chiral mimic of CpFe

Allemann, Christophe ; Jenny, Titus (Dir.)

Thèse de doctorat : Université de Fribourg, 2002 ; No 1369.

Le domaine des composés organométalliques optiquement actifs est plus que jamais un champ d'activité important. Dans ce domaine, le complexe (-)-(1S)-dicarbonyliode[μ5-(2,8,8-triméthylbicyclo[3.2.1]oct-3,6-diµene)2-yle] fer (1), appelé 2-Me-BOD-Fe(CO)2I, se profile comme une nouvelle étape dans le développement de complexes cyclopentadiènyles chiraux apparentés. L'étude de la...

Generation of alkoxyl radicals and their applications for ß-scission reactions in bridged bicyclic systems

Giraud, Anne ; Renaud, Philippe (Dir.) ; Cossy, Janine (Codir.)

Thèse de doctorat : Université de Fribourg, 2000 ; no 1319.

Grâce à leur réactivité particulière et à leurs propriétés caractéristiques, les radicaux alkoxyles constituent un outil puissant de la chimie organique moderne. Parmi leurs transformations typiques, les réactions de β-scission ont retenu notre attention. En effet, la conversion stéréoselective de systèmes bicycliques pontés, permet d’obtenir de nombreux intermédiaires...