Practical Aerobic Oxidation of Alcohols: A Ligand-Enhanced 2,2,6,6-Tetramethylpiperidine-1-oxy/Manganese Nitrate Catalyst System

被引:18
作者
Lagerblom, Kalle [1 ]
Lagerspets, Emi [1 ]
Keskivali, Juha [1 ]
Cook, Chris [1 ]
Ekholm, Filip [1 ]
Parviainen, Arno [1 ]
Repo, Timo [1 ]
机构
[1] Univ Helsinki, Dept Chem, Fac Sci, AI Virtasen Aukio 1,POB 55, FIN-00014 Helsinki, Finland
基金
芬兰科学院;
关键词
alcohols; ligand effects; manganese; oxidation; synthesis design; SELECTIVE OXIDATION; SECONDARY ALCOHOLS; BENZYLIC ALCOHOLS; MANGANESE OXIDE; EFFICIENT; KETONES; OXYGEN; MILD; ALDEHYDES; CARBONYL;
D O I
10.1002/cctc.201700710
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 highly efficient, ligand-enhanced 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO)/Mn(NO3)(2) catalyst system for the aerobic oxidation of alcohols is described. From the series of coordinating ligands studied herein, 2-picolinic acid (PyCOOH) improves the catalytic activity of TEMPO/Mn(NO3)(2) remarkably. Under ambient air at room temperature in acetic acid, the ligand-enhanced catalyst converts aliphatic and benzylic primary alcohols that bear various functional groups into their respective aldehydes with near quantitative conversions. The applicability of the catalyst for convenient preparative synthesis was demonstrated by conducting oxidations on a gram scale. A change of TEMPO to the sterically less demanding 9-azabicyclo[3.3.1]nonane N-oxyl results in a Mn catalyst that is also able to oxidize secondary alcohols to ketones. Mechanistic studies showed that alcohols are oxidized by the oxoammonium cation derived from the nitroxyl radical. The active oxidant is regenerated by Mn(NO3)(2), and this process is greatly promoted by the coordination of PyCOOH to Mn.
引用
收藏
页码:3880 / 3887
页数:8
相关论文
共 73 条
[1]   Aerobic Alcohol Oxidations Mediated by Nitric Acid [J].
Aellig, Christof ;
Girard, Christophe ;
Hermans, Ive .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (51) :12355-12360
[2]   OXIDATION OF DIOLS WITH ALKALI HYPOCHLORITES CATALYZED BY OXAMMONIUM SALTS UNDER 2-PHASE CONDITIONS [J].
ANELLI, PL ;
BANFI, S ;
MONTANARI, F ;
QUICI, S .
JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (12) :2970-2972
[3]  
[Anonymous], 2011, ANGEW CHEM
[4]  
[Anonymous], 2004, ANGEW CHEM-GER EDIT
[5]  
[Anonymous], 2000, SCIENCE, DOI DOI 10.1126/SCIENCE.287.5458.1636
[6]  
[Anonymous], 2007, ADV SYNTH CATAL
[7]  
[Anonymous], 2006, Oxidations of Alcohols to Aldehydes and Ketones
[8]   SELECTIVE OXIDATION OF ALCOHOLS BY A H2O2-RUCL3 SYSTEM UNDER PHASE-TRANSFER CONDITIONS [J].
BARAK, G ;
DAKKA, J ;
SASSON, Y .
JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (15) :3553-3555
[9]   2,5-BIS(1,4-DITHIAFULVEN-6-YL) SUBSTITUTED FURANS, THIOPHENES AND N-METHYL PYRROLES AS PRECURSORS FOR ORGANIC METALS [J].
BENAHMEDGASMI, AS ;
FRERE, P ;
JUBAULT, M ;
GORGUES, A ;
COUSSEAU, J ;
GARRIGUES, B .
SYNTHETIC METALS, 1993, 56 (01) :1751-1755
[10]   Oxoammonium salts. 6. 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate: A stable and convenient reagent for the oxidation of alcohols. Silica gel catalysis [J].
Bobbitt, JM .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (25) :9367-9374