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TEMPO‐Copper(II) Diimine‐Catalysed Oxidation of Benzylic Alcohols in Aqueous Media
Author(s) -
Figiel Paweł J.,
Leskelä Markku,
Repo Timo
Publication year - 2007
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200600505
Subject(s) - diimine , chemistry , benzyl alcohol , benzaldehyde , aqueous solution , copper , alcohol oxidation , deprotonation , catalysis , alcohol , photochemistry , redox , polymer chemistry , organic chemistry , ion
In situ generated copper(II)‐diimine complexes combined with TEMPO (2,2,6,6‐tetramethylpiperidinyl‐1‐oxyl radical) were studied in the oxidation of benzylic alcohols, the focus being on enviromentally benign reaction conditions. In this respect, reactions were studied in aqueous alkaline solutions and dioxygen was used as an end oxidant. This simple catalytic system turned out to be highly efficient and selective in the oxidation of primary and secondary benzylic alcohols to their corresponding carbonyl compounds. Under optimised reaction conditions [5 mol % of TEMPO, 3 mol % of copper( II ) diimine, pH 12.6–13.5, 80 °C, 10 bar O 2 ] benzyl alcohol was quantitatively and selectively oxidised to benzaldehyde. According to ESI‐MS studies, coordination of TEMPO, as well as deprotonated benzyl alcohol to the parent copper‐diimine complex in aqueous solutions is feasible. Supported by these observations a plausible reaction mechanism is proposed for the oxidation reaction.