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Chemicals >> Oxidizing Agents

TEMPO, 2,2,6,6-Tetramethylpiperidinyloxy

2,2,6,6-Tetramethylpiperidinyloxy is a stable nitroxyl radical, which serves in oxidations as catalyst. By substitution in position 4 (4-hydroxy-TEMPO, 4-acetamido-TEMPO) its reactivity can be steered.

For example, processes with oxygen and 5 mol-% TEMPO permit environmentally benign reactions as alternatives to some oxidations, where so far e.g. chrome reagents were used.


Proposed mechanism for the oxidation of primary alcohols under basic conditions
M. Angelin, M. Hermansson, H. Dong, O. Ramström, Eur. J. Org. Chem., 2006, 4323-4326.


Recent Literature


A rapid oxidation of primary and secondary alcohols using catalytic amounts of TEMPO and Yb(OTf)3 in combination with a stoichiometric amount of iodosylbenzene afforded carbonyl compounds in excellent yields without over-oxidation. Oxidation of primary alcohols in the presence of secondary alcohols proceeded with good selectivity.
J.-M. Vatèle, Synlett, 2006, 2055-2058.


An aerobic oxidation of primary and secondary alcohols to aldehydes and ketones using TEMPO-CuCl as catalyst in the ionic liquid [bmin][PF6] has been developed. The system needs no bubbling of O2 due to its good solubility in the ionic liquid. The resulting aldehydes (with no traces of carboxylic acids) and ketones can be extracted with organic solvents. The ionic liquid can be reused after washing with water and drying under high vacuum (8 runs for the oxidation of benzyl alcohol: yields of 72%, 70, 68, 70, 65, 64, 62, and 60).
I. A. Ansari, R. Gree, Org. Lett., 2001, 1507-1509.


The combination of TEMPO and CAN can be used for the aerobic oxidation of benzylic and allylic alcohols into their corresponding carbonyl compounds. However, steric hindrance has been observed to impede the reaction with some substituted allylic systems. The present method is superior to others currently available due to its relatively short reaction times and excellent yields.
S. S. Kim, H. C. Jung, Synthesis, 2003, 2135-2137.


A four-component system consisting of acetamido-TEMPO/Cu(ClO4)2/TMDP/DABCO in DMSO allows an efficient room-temperature aerobic alcohol oxidation of various alcohols into their corresponding aldehydes or ketones in good to excellent yields. The catalytic system can be recycled.
N. Jiang, A. J. Ragauskas, J. Org. Chem., 2006, 71, 7087-7090.


The system Cu(ClO4)2/acetamido-TEMPO/DMAP catalyses the room-temperature aerobic oxidation of primary alcohols to aldehydes in the ionic liquid [bmpy]PF6. The catalysts can be recycled and reused.
N. Jiang, A. J. Ragauskas, Org. Lett., 2005, 7, 3689-3692.


A highly efficient and mild procedure for the oxidation of different types of alcohols uses TEMPO as catalyst, iodobenzene dichloride as stoichiometric oxidant, and pyridine as base. Oxidation of 1,2-diols gives α-hydroxy ketones or α-diketones depending on the amount of oxidant used. High yielding procedures for the preparation of iodoarene dichlorides have been developed.
X.-F. Zhao, C. Zhang, Synthesis, 2007, 551-557.


X.-F. Zhao, C. Zhang, Synthesis, 2007, 551-557.


A highly convenient organocatalytic method for the mono-oxidation of unprotected glycosides relies on the chemoselective properties of TEMPO in combination with trichloroisocyanuric acid under very mild, basic conditions. The resulting dialdo-glycosides are efficiently purified with the use of solid-phase imine capture.
M. Angelin, M. Hermansson, H. Dong, O. Ramström, Eur. J. Org. Chem., 2006, 4323-4326.


An efficient and highly selective method for the oxidative conversion of primary amines to the corresponding nitriles using trichloroisocyanuric acid in the presence of catalytic TEMPO provides a new entry to the synthesis of various aliphatic, aromatic and heterocyclic nitriles in excellent yield.
F.-E. Chen, Y.-Y. Kuang, H.-F. Dai, L. Lu, M. Huo, Synthesis, 2003, 2629-2631.


Iodine was compared to other positive halogens as terminal oxidant in chemoselective oxidations of alcohols using catalytic TEMPO and was shown to be superior in cases of electron-rich and heteroaromatic benzylic alcohols.
R. A. Miller, R. S. Hoerrner, Org. Lett., 2003, 5, 285-287.


A novel, metal-free oxidation system for the catalytic synthesis of aldehydes and ketones using TEMPO and a quarternary ammonium salt as catalysts and Oxone as oxidant proved especially successful for the synthesis of ketones. The mild conditions tolerate even sensitive silyl protective groups which can otherwise be cleaved in the presence of Oxone.
C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000, 2, 1173-1175.


C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000, 2, 1173-1175.


1 mol-% TEMPO and a catalytic amount of 1,3-dibromo-5,5-dimethylhydantoin and NaNO2 is a highly efficient catalytic system for the aerobic oxidations of benzylic alcohols in water.
R. Liu, C. Dong, X. Liang, X. Wang, X. Hu, J. Org. Chem., 2005, 70, 239-244.