Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 2, Pages 259-262Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201604507
Keywords
dioxiranes; lactams; MP2 calculations; oxidation; chemoselectivity
Categories
Funding
- Regione Puglia MIUR PON Ricerca e Competitivita [Avviso 254/Ric., PONa3 00369]
- Universita di Padova [PRAT-CPDA123307, CPDA153122]
- MIUR [PRIN-2010-11 2010CX2TLM_002]
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Dioxiranes are powerful oxidants that can act via two different mechanisms: 1) homolytic (H abstraction and oxygen rebound) and 2) heterolytic (electrophilic oxidation). So far, it has been reported that the nature of the substrate dictates the reaction mode independently from the dioxirane employed. Herein, we report an unprecedented case in which the nature of the dioxirane rules the oxidation chemoselectivity. In particular, a switch from C-H to N-H oxidation is observed in the oxidation of lactams moving from dimethyl dioxirane (DDO) to methyl(trifluoromethyl) dioxirane (TFDO). A physical organic chemistry study, which combines the oxidation with two other dioxiranes methyl(fluoromethyl) dioxirane, MFDO, and methyl(difluoromethyl) dioxirane, DFDO, with computational studies, points to a diverse ability of the dioxiranes to either stabilize the homo or the heterolytic pathway.
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