Jean Rigaudy

Electron-transfer activation. Photochemical N-demethylation of tertiary amines

Abstract DAP2+ sensitized photooxidation of some biologically active N-methylated alkaloids affords the corresponding secondary amines in excellent yields (80-95 %).

Electron-transfer activation. Salt effects on the photooxidation of tertiary amines : A useful N-demethylation method

Abstract Photooxidation of tertiary methylamines sensitized by electron acceptors like 9,10-dicyanoanthracene is shown to proceed by two distinct ways depending on the presence of added salts. In the absence of added salt both nor and N-formyl compounds were obtained while with added salt the nor-derivative is obtained highly efficiently.

Electron transfer activation. Hydroperoxide intermediates in a novel and selective procedure for benzylic oxidations

Abstract A selective and mild photochemical procedure for benzylic oxidations with 9,10-dicyanoanthracene (DCA), an usual electron acceptor, in the presence of methyl viologen (MV 2+ ), an electron relay, has been developed. Methyl and methylene groups are oxidized in good to excellent yields to the corresponding hydroperoxides.

Bicyclic aziridines as intermediates in the photolysis of polycyclic aromatic azides.

Abstract According to the subsequent treatment, azepines 16 , 17 , 19 or 1,2-dihydro derivatives 18 and 20 are obtained in the photolysis in basic medium of β-anthracenic azides 7b and 7c and provide strong evidence for the intermediate formation of bicyclic aziridines.

Rearrangement d'hydroperoxy-3 indolines issues de la photo-oxygenation d'indoles en milieu reducteur

Abstract Trapping by KBH 4 of intermediates formed in the reaction of N-methylindoles with singlet oxygen leads partially to 3-hydroperoxyindolines which undergo in basic methanol an unusual rearrangement to 6-methoxy N-methylindoles.

Une nouvelle methoxylation d'hydroperoxy-3 indolines issues de la photo-oxygenation d'indoles en milieu reducteur

Abstract 3-Hydroperoxy-1,3,6-trimethyl-2-phenyl indolines coming from the sensitized photooxygenation of the indoles in presence of KBH4 rearrange partially in basic methanol into the corresponding 3-hydroxy-6-methoxymethyL indolines.

SAEUREKATALYSIERTE UMLAGERUNGEN VON MESO-PHOTOOXIDEN DER AZENE 2. MITT. PHOTOOXID VON 2-BENZOYL-9,10-DIPHENYL-ANTHRACEN

Die durch Schwefelsaure katalysierte Umlagerung des Peroxids (I) in Essigsaure/ Tetrahydrofuran fuhrt zu den isomeren Ketonen (II) und (III).