Iron Chloride/4‐Acetamido‐TEMPO/Sodium Nitrite‐Catalyzed Aerobic Oxidation of Primary Alcohols to the Aldehydes

Abstract

A variety of 4-substituted 2,2,6,6-tetramethylpiperidyl-1-oxy (TEMPO) derivatives has been screened for their ability in the oxidation of primary alcohols to the aldehydes with dioxygen under mild conditions. An evaluation of the efficiency of these 4-substituted TEMPO derivatives in the alcohol oxidation may allow an insight into the effect of the structural variations of TEMPO on the oxidation of alcohols, which should facilitate catalyst design and screening efforts. Based on the screening results of 4-substituted TEMPO derivatives, the catalyst comprised of 4-acetamido-TEMPO, iron chloride and sodium nitrite, has been developed for the highly efficient oxidation of a wide range of primary alcohols including primary aliphatic alcohols to the corresponding aldehydes under mild conditions.

Solvent-Free Microwave-Assisted Peroxidative Oxidation of Alcohols Catalyzed by Iron(III)-TEMPO Catalytic Systems

“…Iron has become largely used in many oxidation reactions, such as epoxidation [23], sulfoxidation [24], hydroxylation [25], etc. and in the last two decades iron complexes have also been developed to catalyze alcohols oxidations [13,26]. Recently, some iron complexes have been reported by our group [27,28], which effectively catalyze the oxidation reactions of secondary alcohols and cycloalkanes.…”

Room temperature aerobic oxidation of alcohols using CuBr2 with TEMPO and a tetradentate polymer based pyridyl-imine ligand

“…In the interest of sustainability, there has been significant development in the use of more abundant and cheaper transition metals such as iron [18][19] and copper as active catalysts. Following the first reported aerobic oxidation of activated primary alcohols by Semmelhack [20] et al in 1984, inexpensive and abundant copper has attracted much attention in the field of alcohol oxidations.…”

Selective Oxidation of Primary and Secondary Alcohols with Hydrogen Peroxide Promoted by Copper Acetate-TMHPO

“…[1][2][3][4] Traditionally, this transformation has been carried out using toxic agents such as chromium(VI) oxide, 5 dichromate, 6 manganese(IV) oxide, 7 permanganate, 8 tetra-(n-propyl) ammonium perruthenate (TPAP), 9 oxalyl chloride and dimethyl sulfoxide [Swern oxidation], 10 and hypervalent iodine reagents. 11 Furthermore, stoichiometric or excess quantities of these oxidizing agents are required and this often leads to environmental problems.…”