Photosensitized electron transfer oxidation of sulfides: A steady-state study

The photosensitized electron-transfer oxidation of a series of ethyl sulfides RSEt (1, R = C12H25; 2, PhCH2CH 2; 3, PhCH2; 4, PhCMe2; 5, Ph2CH) has been examined in acetonitrile and the product distribution discussed on the basis of the mechanisms proposed. In nitrogen-flushed solutions, cleaved alc...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Bonesi, S.M., Fagnoni, M., Albini, A.
Formato:	JOUR
Materias:	Electron transfer Oxidation Photochemistry Reaction mechanisms Sulfides
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_1434193X_v_n15_p2612_Bonesi
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_1434193X_v_n15_p2612_Bonesi
record_format	dspace
spelling	todo:paper_1434193X_v_n15_p2612_Bonesi2023-10-03T16:14:15Z Photosensitized electron transfer oxidation of sulfides: A steady-state study Bonesi, S.M. Fagnoni, M. Albini, A. Electron transfer Oxidation Photochemistry Reaction mechanisms Sulfides The photosensitized electron-transfer oxidation of a series of ethyl sulfides RSEt (1, R = C12H25; 2, PhCH2CH 2; 3, PhCH2; 4, PhCMe2; 5, Ph2CH) has been examined in acetonitrile and the product distribution discussed on the basis of the mechanisms proposed. In nitrogen-flushed solutions, cleaved alcohols and alkenes are formed, whereas under oxygen, in reactions that are 10-70 times faster, sulfoxides and cleaved aldehydes and ketones are formed in addition to the afore-mentioned products. Two sensitizers are compared, 9,10-dicyanoanthracene (DCA) and 2,4,6-triphenylpyrylium tetrafluoroborate (TPP+BF4-), the former giving a higher proportion of the sulfoxide, the latter of cleaved carbonyls. The sulfoxidation is due to the contribution of the singlet oxygen path with DCA. Oxidative cleavage, on the other hand, occurs both with DCA and with TPP+ which is known to produce neither singlet oxygen nor the superoxide anion. This process involves deprotonation from the α position of the sulfide radical cation, but the TPP+ results suggest that O2.- is not necessarily involved and non-activated oxygen forms a weak adduct with the radical cation promoting α-hydrogen transfer, particularly with benzylic derivatives. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_1434193X_v_n15_p2612_Bonesi
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Electron transfer Oxidation Photochemistry Reaction mechanisms Sulfides
spellingShingle	Electron transfer Oxidation Photochemistry Reaction mechanisms Sulfides Bonesi, S.M. Fagnoni, M. Albini, A. Photosensitized electron transfer oxidation of sulfides: A steady-state study
topic_facet	Electron transfer Oxidation Photochemistry Reaction mechanisms Sulfides
description	The photosensitized electron-transfer oxidation of a series of ethyl sulfides RSEt (1, R = C12H25; 2, PhCH2CH 2; 3, PhCH2; 4, PhCMe2; 5, Ph2CH) has been examined in acetonitrile and the product distribution discussed on the basis of the mechanisms proposed. In nitrogen-flushed solutions, cleaved alcohols and alkenes are formed, whereas under oxygen, in reactions that are 10-70 times faster, sulfoxides and cleaved aldehydes and ketones are formed in addition to the afore-mentioned products. Two sensitizers are compared, 9,10-dicyanoanthracene (DCA) and 2,4,6-triphenylpyrylium tetrafluoroborate (TPP+BF4-), the former giving a higher proportion of the sulfoxide, the latter of cleaved carbonyls. The sulfoxidation is due to the contribution of the singlet oxygen path with DCA. Oxidative cleavage, on the other hand, occurs both with DCA and with TPP+ which is known to produce neither singlet oxygen nor the superoxide anion. This process involves deprotonation from the α position of the sulfide radical cation, but the TPP+ results suggest that O2.- is not necessarily involved and non-activated oxygen forms a weak adduct with the radical cation promoting α-hydrogen transfer, particularly with benzylic derivatives. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
format	JOUR
author	Bonesi, S.M. Fagnoni, M. Albini, A.
author_facet	Bonesi, S.M. Fagnoni, M. Albini, A.
author_sort	Bonesi, S.M.
title	Photosensitized electron transfer oxidation of sulfides: A steady-state study
title_short	Photosensitized electron transfer oxidation of sulfides: A steady-state study
title_full	Photosensitized electron transfer oxidation of sulfides: A steady-state study
title_fullStr	Photosensitized electron transfer oxidation of sulfides: A steady-state study
title_full_unstemmed	Photosensitized electron transfer oxidation of sulfides: A steady-state study
title_sort	photosensitized electron transfer oxidation of sulfides: a steady-state study
url	http://hdl.handle.net/20.500.12110/paper_1434193X_v_n15_p2612_Bonesi
work_keys_str_mv	AT bonesism photosensitizedelectrontransferoxidationofsulfidesasteadystatestudy AT fagnonim photosensitizedelectrontransferoxidationofsulfidesasteadystatestudy AT albinia photosensitizedelectrontransferoxidationofsulfidesasteadystatestudy
_version_	1807320538576584704

Photosensitized electron transfer oxidation of sulfides: A steady-state study

Ejemplares similares