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The Photooxygenation of Benzyl, Heteroarylmethyl, and Allyl Sulfides
Author(s) -
Bonesi Sergio M.,
Torriani Rosangela,
Mella Mariella,
Albini Angelo
Publication year - 1999
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199907)1999:7<1723::aid-ejoc1723>3.0.co;2-r
Subject(s) - chemistry , photooxygenation , sulfide , singlet oxygen , medicinal chemistry , ketone , photochemistry , aldehyde , moiety , acetonitrile , sulfoxide , organic chemistry , catalysis , oxygen
The photosensitised oxidation of benzyl ethyl sulfides in aprotic solvents (benzene or acetonitrile) gives the corresponding aldehydes under mild conditions. This is a general reaction which applies to benzyl derivatives containing either electron‐donating or electron‐withdrawing substituents and furthermore to hetero analogues such as 2‐pyridinylmethyl sulfide (not to the 3‐indolylmethyl sulfide, since reaction at the heterocycle moiety competes) as well as to allyl sulfides. In a protic solvent (methanol) these sulfides give the sulfoxides instead (except for the nitrobenzyl derivatives, where the aldehyde remains the major product). Among the α‐substituted sulfides tested, the α‐phenylbenzyl and the 3‐cyclohexenyl sulfide give the corresponding ketone (the latter in a low yield), but the α‐methylbenzyl sulfide gives the sulfoxide as the main product. The rate for singlet oxygen quenching and for chemical reaction have been measured for representative benzyl sulfides. The reaction is discussed in the frame of the currently accepted mechanism for sulfide photooxygenation. The key step for oxidative C–S bond cleavage appears to be hydrogen transfer from the activated α position in the first formed intermediate, the persulfoxide. This reaction is inhibited in methanol where the persulfoxide is hydrogen‐bonded.