NHPI and ferric nitrate: a mild and selective system for aerobic oxidation of benzylic methylenes

被引：86

作者：

Miao, Chengxia ^{[1
]}

Zhao, Hanqing ^{[2
]}

Zhao, Quanyi ^{[2
]}

Xia, Chungu ^{[1
]}

Sun, Wei ^{[1
]}

机构：

[1] Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China

[2] Lanzhou Univ, Sch Pharm, Lanzhou 730000, Peoples R China

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2016年 / 6卷 / 05期

基金：

中国国家自然科学基金;

关键词：

N-HYDROXYPHTHALIMIDE; MOLECULAR-OXYGEN; METAL-FREE; CATALYTIC-OXIDATION; SECONDARY ALCOHOLS; ORGANIC-COMPOUNDS; TERMINAL ALKYNES; HIGHLY EFFICIENT; NITRIC-ACID; HYDROCARBONS;

D O I：

10.1039/c5cy01245g

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A mild and selective system comprising N-hydroxyphthalimide (NHPI) and Fe(NO3)(3)center dot 9H(2)O was developed for the oxidation of benzylic methylenes with an atmospheric pressure of molecular oxygen at 25 degrees C. The influences of reaction conditions such as solvent, different metal catalysts and catalyst loading were studied, as well as the kinetics of the oxidation reaction. Various benzylic methylene substrates could be oxidized to the corresponding carbonyl compounds in satisfactory yields with this catalytic system. Hammett analysis suggested that the substrates with electron-donating groups would have higher oxidation rates. Isotopic (O-18) labeling experiments provided evidence of the participation of the nitrate anion in the catalytic cycle. In addition, a possible radical mechanism involving hydrogen atom abstraction by PINO (phthalimide-N-oxyl) and nitrate participation for the oxidation of benzylic methylenes in the Fe(NO3)(3)center dot 9H(2)O/NHPI/O-2 system was proposed.

引用

页码：1378 / 1383

页数：6

共 57 条

[1]

[Anonymous], 1990, OXIDATIONS ORGANIC C

[2] Simple mixed Fe-Zn catalysts for the Suzuki couplings of tetraarylborates with benzyl halides and 2-halopyridines [J].

Bedford, Robin B. ;

Hall, Mark A. ;

Hodges, George R. ;

Huwe, Michael ;

Wilkinson, Mark C. .

CHEMICAL COMMUNICATIONS, 2009, (42) :6430-6432

[3] Iron-catalyzed reactions in organic synthesis [J].

Bolm, C ;

Legros, J ;

Le Paih, J ;

Zani, L .

CHEMICAL REVIEWS, 2004, 104 (12) :6217-6254

[4] Transition-metal complexes for liquid-phase catalytic oxidation:: some aspects of industrial reactions and of emerging technologies [J].

Brégeault, JM .

DALTON TRANSACTIONS, 2003, (17) :3289-3302

[5] Metal-free allylic/benzylic oxidation strategies with molecular oxygen: recent advances and future prospects [J].

Chen, Kexian ;

Zhang, Pengfei ;

Wang, Yong ;

Li, Haoran .

GREEN CHEMISTRY, 2014, 16 (05) :2344-2374

[6] The mechanism of the oxidation of benzyl alcohol by iron(III)nitrate: conventional versus microwave heating [J].

Dressen, Mark H. C. L. ;

Stumpel, Jelle E. ;

van de Kruijs, Bastiaan H. P. ;

Meuldijk, Jan ;

Vekemans, Jef A. J. M. ;

Hulshof, Lumbertus A. .

GREEN CHEMISTRY, 2009, 11 (01) :60-64

[7] Oxidation of organic substrates by molecular oxygen mediated by N-hydroxyphthalimide (NHPI) and acetaldehyde [J].

Einhorn, C ;

Einhorn, J ;

Marcadal, C ;

Pierre, JL .

CHEMICAL COMMUNICATIONS, 1997, (05) :447-448

[8] A KINETICS STUDY OF THE OXIDATION OF IRON(II) BY NITRIC-ACID [J].

EPSTEIN, IR ;

KUSTIN, K ;

WARSHAW, LJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (11) :3751-3758

[9] Osmium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen [J].

Esteruelas, Miguel A. ;

Garcia-Obregon, Tania ;

Herrero, Juana ;

Olivan, Montserrat .

ORGANOMETALLICS, 2011, 30 (23) :6402-6407

[10]

Fukuda O, 2001, ADV SYNTH CATAL, V343, P809, DOI 10.1002/1615-4169(20011231)343:8<809::AID-ADSC809>3.0.CO

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