General and Efficient a-Oxygenation of Carbonyl Compounds by TEMPO Induced by Single-Electron-Transfer Oxidation of Their Enolates

0384909 - ÚOCHB 2013 RIV DE eng J - Článek v odborném periodiku
Dinca, E. - Hartmann, P. - Smrček, Jakub - Dix, I. - Jones, P. G. - Jahn, Ullrich
General and Efficient a-Oxygenation of Carbonyl Compounds by TEMPO Induced by Single-Electron-Transfer Oxidation of Their Enolates.
European Journal of Organic Chemistry. -, č. 24 (2012), s. 4461-4482. ISSN 1434-193X. E-ISSN 1099-0690
Institucionální podpora: RVO:61388963
Klíčová slova: carbonyl compounds * oxidation * radicals * electron transfer * enolates
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 3.344, rok: 2012

A generally applicable method for the synthesis of protected a-oxygenated carbonyl compounds is reported. It is based on the single-electron-transfer oxidation of easily generated enolates to the corresponding a-carbonyl radicals. Coupling with the stable free radical TEMPO provides a-(piperidinyloxy) ketones, esters, amides, acids or nitriles in moderate-to-excellent yields. Enolate aggregates influence the outcome of the oxygenation reactions significantly. Competitive reactions have been analyzed and conditions for their minimization are presented. Chemoselective reduction of the products led to either NO bond cleavage to a-hydroxy carbonyl compounds or reduction of the carbonyl functionality tomonoprotected 1,2-diols or O-protected amino alcohols.
Trvalý link: http://hdl.handle.net/11104/0214372