Oxidation of alcohols to aldehydes with oxygen and cupric ion, mediated by nitrosonium ion

Semmelhack, M. F.; Schmid, Christopher R.; Cortés, David A.; Chou, Chuen S.

doi:10.1021/ja00323a064

Cited by 616 publications

(376 citation statements)

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“…Even when we increased the reaction time to 24 h, the yields did not improve significantly. This might be explained by the presence of aliphatic aldehydes and oxygen which could lead to decomposition of the oxoammonium ion in our catalytic cycle and therefore decrease the overall catalytic activity [20]. We were pleased to find that benzylic secondary alcohols could also be oxidized to ketones.…”

Section: Aerobic Oxidation Of Other Primary and Secondary Alcohols Inmentioning

confidence: 93%

“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Kerton

2012

Applied Catalysis A: General

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Abstract.A series of tetradentate pyridyl-imine terminated Schiff-base ligands has been investigated for their ability in the catalytic oxidation of alcohols when combined with copper bromide (CuBr 2 ) and 2,2,6,6-tetramethylpiperidyl-1-oxy (TEMPO). Analogous bidentate ligands showed poorer catalytic activity and the ratio of Cu:ligand was of crucial importance in maintaining high yields. The polydimethylsiloxane (PDMS) derived pyridyl-imine terminated ligand combined with copper (II) ions affords an effective and selective catalyst for aerobic oxidations of primary and secondary alcohols under aqueous conditions. Preliminary mechanistic studies suggest that bimetallic complexes may be playing a role in the catalytic transformation. Graphical Abstract1

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Section: Aerobic Oxidation Of Other Primary and Secondary Alcohols Inmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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

Kerton

2012

Applied Catalysis A: General

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“…Even if this article is not the first dealing with oxidation of alcohols by TEMPO, 32 Semmelhack et al (1984) showed that selective oxidation of primary alcohol, in the presence 33 of secondary ones, was feasible. The oxidation of primary alcohol groups of partially 34 protected glycosides carbohydrates was then firstly published by Davis et al (1993).…”

Section: Introduction 28mentioning

confidence: 96%

TEMPO-mediated oxidation of polysaccharides: An ongoing story

Pierre

Punta

Delattre

et al. 2017

Carbohydrate Polymers

128

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15The oxidation of natural polysaccharides by TEMPO has become by now an "old chemical 16 reaction" which led to numerous studies mainly conducted on cellulose. This regioselective 17 oxidation of primary alcohol groups of neutral polysaccharides has generated a new class of 18 polyuronides not identified before in nature, even if the discovery of enzymes promoting an 19 analogous oxidation has been more recently reported. Around the same time, the scientific 20 community discovered the surprising biological and techno-functional properties of these 21 anionic macromolecules with a high potential of application in numerous industrial fields. The 22 objective of this review is to establish the state of the art of TEMPO chemistry applied to 23 polysaccharide oxidation, its history, the resulting products, their applications and the 24 associated modifying enzymes. 25

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“…These authors utilized a CuCl/TEMPO system in DMF (N,N-dimethylformamide) to furnish the aerobic oxidation of benzylic and allylic alcohols. 11 Recent progress indicates that both Cu(I) and Cu(II) complexes with a N,N-or N,O-ligands in combination with TEMPO could be efficient catalysts or catalyst precursors for the aerobic oxidation of various alcohols, and of particular note is a highly efficient copper/2,2'-bipyridine/TEMPO system developed by the Stahl group. [12][13][14][15][16][17] However, the types of organic ligands exploited in the copper catalyst systems are still limited and the structures of copper catalysts involved in the catalytic process are rarely explored.…”

Section: Introductionmentioning

confidence: 99%

Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

et al. 2014

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ARTICLE This journal is © The Royal Society of Chemistry 2013J. Name., 2013, 00, 1-3 | 1 The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1:1:1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)-1 in high yield. The single crystal structure of (R)-1 reveals a tetranuclear copper(II) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-2; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)-1 and (S,R)-2 have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)-1 selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (up to 770) in the air, while (S,R)-2 exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)-1 and (S,R)-2 in controlling the reactivity towards aerobic oxidation reactions is discussed. IntroductionThe oxidation of alcohols to carbonyl compounds is an important transformation in synthetic organic chemistry and extensive efforts have been focused on the development of atom-economic oxidation methodologies for such reactions. [1][2][3][4] Amongst the protocols developed to date, catalytic aerobic oxidation has proven to be especially efficient and valuable by virtue of the use of a low-loaded, low-cost catalyst and molecular oxygen from the air. [5][6][7][8][9][10] In the past two decades, copper-catalysed, TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) mediated aerobic oxidation has been the most popular choice of catalyst systems since the pioneering work of Semmelhack and coworkers in 1984. These authors utilized a CuCl/TEMPO system in DMF (N,N-dimethylformamide) to furnish the aerobic oxidation of benzylic and allylic alcohols. 11 Recent progress indicates that both Cu(I) and Cu(II) complexes with a N,N-or N,O-ligands in combination with TEMPO could be efficient catalysts or catalyst precursors for the aerobic oxidation of various alcohols, and of particular note is a highly efficient copper/2,2'-bipyridine/TEMPO system developed by the Stahl group. 12-17 However, the types of organic ligands exploited in the copper catalyst systems are still limited and the structures of copper catalysts involved in the catalytic process are rarely explored. [17][18][19][20] The construction of metal-organic cluster compounds through self-assembly of predesigned ligands with appropriate metal ions is a prime research topic [21][22][23][24][25] Herein, we report the one-pot syntheses and crystal structures of two tetranuclear and dinuclear copper(II) complexes resulting from the in situ synthesis of chiral Schiff base ligands (Scheme 1), and their catalytic ap...

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Oxidation of alcohols to aldehydes with oxygen and cupric ion, mediated by nitrosonium ion

Cited by 616 publications

References 2 publications

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

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

TEMPO-mediated oxidation of polysaccharides: An ongoing story

Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

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