Oxidation of diols with alkali hypochlorites catalyzed by oxammonium salts under two-phase conditions

Anelli, Pier Lucio; Banfi, Stefano; Montanari, Fernando; Quici, Silvio

doi:10.1021/jo00273a038

Cited by 220 publications

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“…Efficient methods for the conversion of alcohols to aldehydes, ketones or carboxylic acids under mild conditions have been developed, using TEMPO (2,2,6, 6-tetramethyl-1-piperidinyloxy), (I), as a catalyst and （I） stoichiometric amounts of inexpensive, safe and easy to handle oxidants such as bleach [2], [bis(acetoxy) iodo] benzene (BAIB) [3], trichloroisocyanuricacid (TCCA) [4], oxone [5] or iodine [6].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization of Cellulose Grafted N-Oxide Reagent and Its Application in Oxidation of Alkyl/Aryl Halides

Kaur¹,

Dhiman²

2011

IJOC

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Oxidation of aliphatic and aromatic halides by N-oxide functionalities supported on 4-vinyl pyridine, (4-VP), grafted cellulose is reported in the present manuscript. Synthesis of graft copolymer of cellulose and poly 4-vinyl pyridine, poly(4-VP), has been carried out using ceric ions as redox initiator. Post-grafting treatment of CellO-g-poly(4-VP) with 30% H 2 O 2 in acetic acid gives Cellulose-g-poly(4-VP) N-oxide, the polymeric supported oxidizing reagent. The polymeric support, CellO-g-poly(4-VP) N-oxide, has been used for oxidation of different alkyl/aryl halide such as 1-bromo-3-methyl butane, 2-bromo propane, 1-bromo heptane and benzyl chloride. The polymeric reagent was characterized by IR and thermo-gravimetric analysis. The oxidized products were characterized by FTIR and H 1 NMR spectral methods. The reagent was reused for the oxidation of a fresh alkyl/aryl halides and it was observed that the polymeric reagent oxidizes the compounds successfully but with little lower product yield.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization of Cellulose Grafted N-Oxide Reagent and Its Application in Oxidation of Alkyl/Aryl Halides

Kaur¹,

Dhiman²

2011

IJOC

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“…Thus, the laccase was combined with 4-hydroxy-TEMPO (4-OH-TEMPO), but in this case just 5% conversion was achieved after 24 h. Several mixtures of oxidant(s) and TEMPO were tried in aqueous media such as NaOCl (9 equiv. ), 28 31 or iodine (1.5 equiv. ), 32 but negligible or very low conversions were attained.…”

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Laccase/TEMPO-mediated system for the thermodynamically disfavored oxidation of 2,2-dihalo-1-phenylethanol derivatives

et al. 2014

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COMMUNICATION This journal is © The Royal Society of Chemistry 2012Green Chemistry, 2014, 00, 1-5 | 1 An efficient methodology to oxidize β,β-dihalogenated secondary alcohols employing oxygen was achieved in a biphasic medium using the laccase from Trametes versicolor/TEMPO pair, providing the corresponding ketones in a clean fashion under very mild conditions. Moreover, a chemoenzymatic protocol has been successfully applied to deracemize 2,2-dichloro-1-phenylethanol combining this oxidation with an alcohol dehydrogenase-catalyzed bioreduction.Oxidation of alcohols into the corresponding carbonylic compounds is one of the fundamental reactions in organic chemistry. Traditionally these transformations comprised the use of hazardous metal-based reagents in stoichiometric amount, however catalytic methodologies employing oxygen (or air) as mild oxidant in aqueous medium are being recognized for large scale applications, and therefore they are currently emerging as potent competitors.

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“…1], has been extensively used as a catalyst for the oxidation of alcohols in a wide range of chemistry. [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] In particular, TEMPO-catalyzed alcohol oxidation has high priority in the pharmaceutical industry as an efficient, mild, and environmentally acceptable method. However, TEMPO is often inefficient in the oxidation of structurally hindered alcohols, posing a problem in the oxidation of secondary alcohols.…”

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“…27,28) The catalytic activity of Nor-AZADO was compared with those of TEMPO, AZADO, 1-Me-AZADO, and ABNO under Anelli's condition using NaOCl as the bulk oxidant 12,13) (Tables 1, 2). The catalytic activities toward secondary alcohols are shown in Table 1.…”

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confidence: 99%

“…The primary alcohols 12 and 23 were also oxidized to their corresponding aldehyde 13 and 24 in high yield (entries 11,12), although the oxidation of p-nitrobenzyl alcohol (25) to p-nitrobenzylaldehyde (26) resulted in moderate yield because of the overoxidation of (26) to the carboxylic acid (27) (entry 13). Note that the hydrobenzoin (28), which is prone to form benzaldehyde because of its easy carbon-carbon bond cleavage in some other oxidation systems, 30) was oxidized to benzil (29) in quantitative yield without oxidative cleavage (entry 14).…”

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9-Azanoradamantane N-Oxyl (Nor-AZADO): A Highly Active Organocatalyst for Alcohol Oxidation

et al. 2011

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A highly active organocatalyst for alcohol oxidation has been developed. 9-Azanoradamantane N-oxyl (Nor-AZADO 4), constituting an unhindered, stable nitroxyl radical, exhibits superior catalytic activity to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and AZADOs in the oxidation of alcohols to their corresponding carbonyl compounds.Key words organocatalyst; nitroxyl radical; alcohol oxidation; aerobic oxidation; 2-azaadamantane N-oxyl AZADO The oxidation of alcohols to their corresponding carbonyl compounds is one of the most fundamental transformations in both laboratory synthesis and industrial manufacturing, and numerous methods of such oxidation have been developed.1,2) In recent years, a stable class of nitroxyl radicals, as exemplified by TEMPO [2,2,6,6-tetramethyl piperidinyl 1-oxyl (1); Fig. 1], has been extensively used as a catalyst for the oxidation of alcohols in a wide range of chemistry. [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] In particular, TEMPO-catalyzed alcohol oxidation has high priority in the pharmaceutical industry as an efficient, mild, and environmentally acceptable method. However, TEMPO is often inefficient in the oxidation of structurally hindered alcohols, posing a problem in the oxidation of secondary alcohols.We have recently reported that a less-hindered class of nitroxyl radicals, namely, 2-azaadamantane N-oxyls [AZADOs; AZADO (2a) and 1-Me-AZADO (2b)] and 9-azabicyclo[3.3.1]nonane N-oxyl [ABNO (3)], exhibit significantly enhanced reactivity compared with TEMPO.20-26) They exhibit extremely high activities toward a wide range of alcohols, including structurally hindered secondary alcohols that TEMPO fails to efficiently oxidize. 20,21) A structure-activity comparison indicated that the steric congestion near the active center exerts a critical impact on catalytic efficiency. 20) In our continuous interest in nitroxyl-radical-based oxidation, we envisaged that the catalytic activity of nitroxyl radicals can further be enhanced by reducing the steric factors around their active center. We herein report the advanced catalytic activity of 9-azanoradamantane N-oxyl [Nor-AZADO (4); Fig. 1]. This new catalyst exhibits superior catalytic efficiency to AZADO, 1-Me-AZADO and ABNO as well as to TEMPO.Nor-AZADO (4) was firstly synthesized in 1978 by Dupeyre and Rassat and reported to be a stable class of nitroxyl radicals.27) To the best of our knowledge, however, no study of Nor-AZADO has been reported since then. We were particularly interested in determining whether Nor-AZADO, which is a constraint variant of AZADO, produces the oxoammonium ions, which are useful for alcohol oxidation.Nor-AZADO was prepared in five steps from acetonedicarboxylic acid (5), glutaraldehyde, and benzylamine, by a previous method (Chart 1) with slight modification.

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Oxidation of diols with alkali hypochlorites catalyzed by oxammonium salts under two-phase conditions

Cited by 220 publications

References 1 publication

Synthesis, Characterization of Cellulose Grafted N-Oxide Reagent and Its Application in Oxidation of Alkyl/Aryl Halides

Synthesis, Characterization of Cellulose Grafted N-Oxide Reagent and Its Application in Oxidation of Alkyl/Aryl Halides

Laccase/TEMPO-mediated system for the thermodynamically disfavored oxidation of 2,2-dihalo-1-phenylethanol derivatives

9-Azanoradamantane N-Oxyl (Nor-AZADO): A Highly Active Organocatalyst for Alcohol Oxidation

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