Abstract
4,5-Dihydro-1,2,3-oxadiazoles are postulated to be key intermediates in the industrial synthesis of ketones from alkenes, in the alkylation of DNA in vivo, and in the decomposition of N-nitrosoureas; they are also a subject of great interest for theoretical chemists. In the presented report, the formation of 4,5-dihydro-1,2,3-oxadiazole and the subsequent decay into secondary products have been studied by NMR monitoring analysis. The elusive properties evading characterization have now been confirmed by H-1, C-13, and N-15 NMR spectroscopy, and relevant 2D experiments at very low temperatures. Our experiments with suitably substituted N-nitrosoureas using thallium(I) alkoxides as bases under apolar conditions answer important questions on the existence and the secondary products of 4,5-dihydro-1,2,3-oxadiazole.
| Original language | English |
|---|---|
| Pages (from-to) | 15092-+ |
| Number of pages | 8 |
| Journal | CHEMISTRY-A EUROPEAN JOURNAL |
| Volume | 21 |
| Issue number | 43 |
| DOIs | |
| Publication status | Published - 19 Oct 2015 |
| Externally published | Yes |
Cite this
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4,5-Dihydro-1,2,3-oxadiazole : A Very Elusive Key Intermediate in Various Important Chemical Transformations. / Banert, Klaus; Singh, Neeraj; Fiedler, Benjamin; Friedrich, Joachim; Korb, Marcus; Lang, Heinrich.
In: CHEMISTRY-A EUROPEAN JOURNAL, Vol. 21, No. 43, 19.10.2015, p. 15092-+.Research output: Contribution to journal › Article
TY - JOUR
T1 - 4,5-Dihydro-1,2,3-oxadiazole
T2 - A Very Elusive Key Intermediate in Various Important Chemical Transformations
AU - Banert, Klaus
AU - Singh, Neeraj
AU - Fiedler, Benjamin
AU - Friedrich, Joachim
AU - Korb, Marcus
AU - Lang, Heinrich
PY - 2015/10/19
Y1 - 2015/10/19
N2 - 4,5-Dihydro-1,2,3-oxadiazoles are postulated to be key intermediates in the industrial synthesis of ketones from alkenes, in the alkylation of DNA in vivo, and in the decomposition of N-nitrosoureas; they are also a subject of great interest for theoretical chemists. In the presented report, the formation of 4,5-dihydro-1,2,3-oxadiazole and the subsequent decay into secondary products have been studied by NMR monitoring analysis. The elusive properties evading characterization have now been confirmed by H-1, C-13, and N-15 NMR spectroscopy, and relevant 2D experiments at very low temperatures. Our experiments with suitably substituted N-nitrosoureas using thallium(I) alkoxides as bases under apolar conditions answer important questions on the existence and the secondary products of 4,5-dihydro-1,2,3-oxadiazole.
AB - 4,5-Dihydro-1,2,3-oxadiazoles are postulated to be key intermediates in the industrial synthesis of ketones from alkenes, in the alkylation of DNA in vivo, and in the decomposition of N-nitrosoureas; they are also a subject of great interest for theoretical chemists. In the presented report, the formation of 4,5-dihydro-1,2,3-oxadiazole and the subsequent decay into secondary products have been studied by NMR monitoring analysis. The elusive properties evading characterization have now been confirmed by H-1, C-13, and N-15 NMR spectroscopy, and relevant 2D experiments at very low temperatures. Our experiments with suitably substituted N-nitrosoureas using thallium(I) alkoxides as bases under apolar conditions answer important questions on the existence and the secondary products of 4,5-dihydro-1,2,3-oxadiazole.
KW - alkylation
KW - cycloreversion
KW - NMR
KW - spectroscopy
KW - nucleophilic substitution
KW - reactive intermediates
KW - AUXILIARY BASIS-SETS
KW - BETA-OXIDIZED NITROSAMINES
KW - NUCLEAR-MAGNETIC-RESONANCE
KW - LIQUID-PHASE OXIDATION
KW - N-NITROSO COMPOUNDS
KW - AQUEOUS DECOMPOSITION
KW - AB-INITIO
KW - 1,3-DIPOLAR CYCLOADDITION
KW - NMR-SPECTRA
KW - OXIDE
U2 - 10.1002/chem.201502326
DO - 10.1002/chem.201502326
M3 - Article
VL - 21
SP - 15092-+
JO - CHEMISTRY-A EUROPEAN JOURNAL
JF - CHEMISTRY-A EUROPEAN JOURNAL
SN - 0947-6539
IS - 43
ER -