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Copper Complexes as Functional Models for Dopamine β‐Hydroxylase – Mechanistic Study of Oxygen Atom Transfer from Cu/O Species to Benzylic C−H Bonds
Author(s) -
Blain Ingrid,
Giorgi Michel,
De Riggi Innocenzo,
Réglier Marius
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20011)2001:1<205::aid-ejic205>3.0.co;2-u
Subject(s) - chemistry , substituent , electrophile , copper , oxygen atom , ligand (biochemistry) , oxygen , stereochemistry , medicinal chemistry , photochemistry , organic chemistry , molecule , catalysis , receptor , biochemistry
The mechanism of the oxygen atom transfer reaction mediated by copper‐oxygen species has been studied through a substrate‐binding ligand approach. Oxidations of copper 5‐X‐IndPY2 type complexes in which an electron donating (X = OMe) or withdrawing group (X = CN) substitutes the aromatic nucleus in position 5, lead to compounds 2b,c and 3b,c resulting from benzylic hydroxylations. With these complexes, where one of the benzylic positions is influenced by a para substituent (leading to 2b,c ) while the other suffers influence from the meta group (leading to 3b,c ), we observe that the ratio 2 : 3 > 1 is in favor of a certain electrophilicity of the copper/oxygen species responsible for the hydroxylations. While a concerted mechanism cannot be excluded, the results are in favor of a two‐step mechanism involving radical species.