Alcohol oxidation with H2O2 catalyzed by a cheap and promptly available imine based iron complex

被引:30
作者
Olivo, Giorgio [1 ,2 ,3 ,4 ]
Giosia, Simone [1 ,2 ]
Barbieri, Alessia [1 ,2 ]
Lanzalunga, Osvaldo [1 ,2 ]
Di Stefano, Stefano [1 ,2 ]
机构
[1] Univ Roma La Sapienza, Dipartimento Chim, Ple A Moro 5, I-00185 Rome, Italy
[2] Univ Roma La Sapienza, Dipartimento Chim, Sez Meccanismi Reaz, Ist CNR Metodol Chim IMC CNR, Ple A Moro 5, I-00185 Rome, Italy
[3] Univ Girona, IQCC, Campus Montilivi, Girona 17071, Spain
[4] Univ Girona, Dept Quim, Campus Montilivi, Girona 17071, Spain
关键词
C-H OXIDATION; NONHEME IRON; SECONDARY ALCOHOLS; AEROBIC OXIDATION; SELECTIVE OXIDATION; HYDROXYLATION; ALDEHYDES; KETONES; METATHESIS; PICOLINATE;
D O I
10.1039/c6ob01984f
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
We previously reported that the iminopyridine iron(II) complex 1, easily and quantitatively obtainable in situ, can activate H2O2 to form a powerful oxidant, capable of aliphatic C-H bond hydroxylation. In the present study we expand the application of this catalyst to the oxidation of a series of alcohols to the corresponding carbonyl compounds. The oxidation of aliphatic alcohols proceeds smoothly, while that of benzylic alcohols is shown to be challenging. Some collected pieces of evidence suggest a preference of the oxidizing species for the aromatic ring instead for the alcoholic moiety. The decrease of the electron density in the aromatic ring shifts the oxidation from the aromatic towards the alcoholic moiety. Quite surprisingly, preferential oxidation of cyclohexanol versus benzylic alcohol was achieved, showing unprecedented selectivity.
引用
收藏
页码:10630 / 10635
页数:6
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