Novel Model Sulfur Compounds as Mechanistic Probes for Enzymatic and Biomimetic Oxidations

ALICIA B. PEÑÉÑORY; JUAN E. ARGÜELLO; MARCELO PUIATTI

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY

WILEY-VCH Verlag GmbH & Co.

Lugar: Weinheim, Alemania; Año: 2005 vol. 2005 p. 114 - 114

1434-193X

o test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH3SCHPh2(2), PhSCH2CH=CH2(3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3-5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS·), whereas 2·+ afforded both fragmentation and mainly. Photochemical treatment of the sulfides 1a and 1b with C(NO2)4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and