PALLADIUM(II)-CATALYZED ASYMMETRIC OXIDATIVE CYCLIZATION OF 2-ALLYLPHENOLS IN THE PRESENCE OF COPPER(II) ACETATE AND MOLECULAR-OXYGEN - STUDY OF THE CATALYSIS OF THE WACKER-TYPE OXIDATION
PALLADIUM(II)-CATALYZED ASYMMETRIC OXIDATIVE CYCLIZATION OF 2-ALLYLPHENOLS IN THE PRESENCE OF COPPER(II) ACETATE AND MOLECULAR-OXYGEN - STUDY OF THE CATALYSIS OF THE WACKER-TYPE OXIDATION
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DOI：
10.1021/ja00399a030
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发表时间：
1981-01-01
影响因子：
15
通讯作者：
MURAHASHI, SI
中科院分区：
文献类型：
--
作者：
HOSOKAWA, T;UNO, T;MURAHASHI, SI
The intramolecular oxidative cyclization of f/ww-2-(2-butenyl) phenol (2) using (+)-(3, 2, 10-? j-pinene) palladium (II) acetate (1) in the pressure of Cu (OAc) 2 and 02 has been studied in order to gain insight into the catalysis of the Wacker-type oxidation. The main results obtained are as follows:(1) the catalytically active Pd (II) species which is different from complex 1 is formed during the reaction,(2) the chiral pinanyl ligand is retained by the catalyst throughout the reaction, and (3) the catalyst consists of copper and palladium linked with an acetate bridge. These results cannot be accounted for by the conventional Wacker-type catalysis involving the reoxidation of palladium (O). A hydroperoxopalladium (II) species coupled with copper (II) acetate is most likely the active catalyst in the present reaction. A mechanism for the enantioselection is also described in comparison with the results obtained by the oxidative cyclizationof m-2-(2-butenyl) phenol.
