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Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert ‐Butyl Hydroperoxide
Author(s) -
van der Toorn John C.,
Kemperman Gerjan,
Sheldon Roger A.,
Arends Isabel W. C. E.
Publication year - 2011
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/ejoc.201100487
Subject(s) - chemistry , diselenide , diphenyl diselenide , catalysis , alcohol , benzyl alcohol , aldehyde , tert butyl hydroperoxide , substrate (aquarium) , alcohol oxidation , selectivity , organic chemistry , medicinal chemistry , selenium , oceanography , geology
We have investigated the Ph 2 Se 2 ‐catalysed oxidation of alcohols with tert ‐butyl hydroperoxide (TBHP) by using a variety of spectroscopic techniques and reaction calorimetry. We showed that the active oxidant is benzeneseleninic anhydride (BSA), formed by reaction of Ph 2 Se 2 with TBHP. The influence of aromatic substituents on the activity of a selection of nine aromatic diselenides involved in alcohol oxidations was studied. Calorimetric experiments showed that compounds that are activated more rapidly have higher initial activity in the catalytic oxidation of benzyl alcohol. An exception to this rule was observed when the diselenide contained a dimethylamino group in the ortho position, which can apparently compensate for its slow pre‐activation by a special ortho effect. An aliphatic alcohol, 1‐decanol was also used as a substrate. Besides diphenyl diselenide only three of the substituted diaryl diselenides studied showed reasonable activity after pre‐activation with TBHP. Dimesityl diselenide displayed the highest activity and selectivity for the oxidation of 1‐decanol. Specificity for a given aldehyde could be achieved by using an oxidant and substrate feed protocol.