Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using Ruthenium/TEMPO as the Catalytic System

Dijksman, A.; Marino-González, Arturo; Payeras, Antoni Mairata i; Arends, Isabel W. C. E.; Sheldon, Roger A.

doi:10.1021/ja0103804

Cited by 517 publications

(273 citation statements)

References 68 publications

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“…The fact that only aldehyde products were selectively formed and no corresponding carboxylic acid products detected is likely due to the known ability of TEMPO to scavenge free radicals, preventing the aldehydes from further auto-oxidation. 18,46,47 It was recently reported that copper(II) complexes of a terpyridine derived ligand catalyzed the aerobic oxidation of benzylic alcohols in aqueous basic media with up to 94% yield. 18,48 Initially, we performed the oxidation of benzylic alcohol by using copper complex (R)-1 as catalyst with a low load (0.25%) at room temperature and a 0.2 M of K 2 CO 3 solution in water as reaction media in the presence of TEMPO (5 mol%), by taking advantage of water as a green solvent.…”

Section: Catalytic Studiesmentioning

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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Section: Catalytic Studiesmentioning

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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“…TEMPO is also broadly employed in organic synthesis for the oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones. Recently, TEMPO catalytic systems (e.g., ruthenium/TEMPO and copper/TEMPO) were reported to enable efficient oxidation of a broad range of primary alcohols, which facilitated their widespread use in synthetic chemistry (Dijksman et al, 2001;Hoover and Stahl, 2011).…”

Section: Introductionmentioning

confidence: 99%

Nitroxide TEMPO: A genotoxic and oxidative stress inducer in cultured cells

Guo

Mittelstaedt

Guo

et al. 2013

Toxicology in Vitro

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Abstract2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) is a low molecular weight nitroxide and stable free radical. In this study, we investigated the cytotoxicity and genotoxicity of TEMPO in mammalian cells using the mouse lymphoma assay (MLA) and in vitro micronucleus assay. In the absence of metabolic activation (S9), 3 mM TEMPO produced significant cytotoxicity and marginal mutagenicity in the MLA; in the presence of S9, treatment of mouse lymphoma cells with 1-2 mM TEMPO resulted in dose-dependent decreases of the relative total growth and increases in mutant frequency. Treatment of TK6 human lymphoblastoid cells with 0.9-2.3 mM TEMPO increased the frequency of both micronuclei (a marker for clastogenicity) and hypodiploid nuclei (a marker of aneugenicity) in a dose-dependent manner; greater responses were produced in the presence of S9. Within the dose range tested, TEMPO induced reactive oxygen species and decreased glutathione levels in mouse lymphoma cells. In addition, the majority of TEMPO-induced mutants had loss of heterozygosity at the Tk locus, with allele loss of ≤34 Mbp.These results indicate that TEMPO is mutagenic in the MLA and induces micronuclei and hypodiploid nuclei in TK6 cells. Oxidative stress may account for part of the genotoxicity induced by TEMPO in both cell lines.

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“…The selective oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones is an important and pivotal reaction in organic synthesis [1][2][3][4] 25 , air/ruthenium cluster 26 , air/copper−bisisoquinoline 27 , air/ruthenium/TEMPO 28 , and polymer−bound Co−oxidants in the presence of TEMPO catalyst 29 are some of the oxidants which have been utilized for such transformation. However, most of the mentioned protocols suffer from several drawbacks in terms of harsh reaction conditions, use of expensive volatile organic solvents, high cost, instability, high toxicity and operational difficulty.…”

Section: Introductionmentioning

confidence: 99%

Activated charcoal: a highly efficient promoter for selective oxidation of alcohols to aldehydes and ketones by K2S2O8 at solvent-free conditions

Safari¹,

Zeynizadeh²

2015

10.5267/j.ccl

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Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using Ruthenium/TEMPO as the Catalytic System

Cited by 517 publications

References 68 publications

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

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

Nitroxide TEMPO: A genotoxic and oxidative stress inducer in cultured cells

Activated charcoal: a highly efficient promoter for selective oxidation of alcohols to aldehydes and ketones by K2S2O8 at solvent-free conditions

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