Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by
            <scp>TEMPO</scp>
            and Bleach: 4‐Methoxyphenylacetic Acid

Zhao, Mangzhu; Li, Jing; Mano, Eiichi; Song, Zhiguo J.; Tschaen, David M.

doi:10.1002/0471264229.os081.21

Cited by 37 publications

(35 citation statements)

References 12 publications

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“…[c] [19] Simply changing chiral amine catalyst to ent-5 a for the catalytic enantioselective allylation reaction step consequently gives access to ent-12 o. We also wanted to investigate the importance of degassing the solvents prior to the co-catalytic enantioselective reaction and found that this was not the case (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

Direct Regiospecific and Highly Enantioselective Intermolecular α‐Allylic Alkylation of Aldehydes by a Combination of Transition‐Metal and Chiral Amine Catalysts

Afewerki¹,

Ibrahem²,

Rydfjord³

et al. 2012

Chemistry A European J

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The first direct intermolecular regiospecific and highly enantioselective α-allylic alkylation of linear aldehydes by a combination of achiral bench-stable Pd(0) complexes and simple chiral amines as co-catalysts is disclosed. The co-catalytic asymmetric chemoselective and regiospecific α-allylic alkylation reaction is linked in tandem with in situ reduction to give the corresponding 2-alkyl alcohols with high enantiomeric ratios (up to 98:2 e.r.; e.r.=enantiomeric ratio). It is also an expeditious entry to valuable 2-alkyl substituted hemiacetals, 2-alkyl-butane-1,4-diols, and amines. The concise co-catalytic asymmetric total syntheses of biologically active natural products (e.g., Arundic acid) are disclosed.

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Section: Resultsmentioning

confidence: 99%

Direct Regiospecific and Highly Enantioselective Intermolecular α‐Allylic Alkylation of Aldehydes by a Combination of Transition‐Metal and Chiral Amine Catalysts

Afewerki¹,

Ibrahem²,

Rydfjord³

et al. 2012

Chemistry A European J

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“…in aqueous acetonitrile. [42] TEMPO in combination with NaOCl generates the oxoammonium salt, which oxidizes the alcohol to the corresponding aldehyde as described above. In a subsequent process the aldehyde further reacts with NaOCl 2 to give the acid and NaOCl, which eventually acts as the oxidant in the reaction with TEMPOH to regenerate TEMPO + (10).…”

Section: Oxidation Of Alcoholsmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

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“…In each of these contributions, concise but thorough discussions of the following methods are given: (1) the preparation of a specific oxoammonium salt ([TEMP=O] + [BF 4 ] − ) and its use for the oxidation of geraniol; 12 (2) nitroxidecatalyzed oxidations using sodium hypochlorite; 13 (3) nitroxide-catalyzed oxidations using a catalytic amount of sodium hypochlorite with sodium chlorite as the secondary oxidant; 14 and (4) nitroxide-catalyzed oxidations using bis(acetoxy)iodobenzene (PhI(OAc) 2 ) as the secondary oxidant. 15 Comprehensive reviews have appeared on the chemistry of oxoammonium salts 10,16 -20 and on oxoammonium ion reactions.…”

Section: Introductionmentioning

confidence: 99%

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by TEMPO and Bleach: 4‐Methoxyphenylacetic Acid

Abstract: 4‐Methoxyphenethyl alcohol 4‐Methoxyphenylacetic acid 2,2,6,6,‐Tetramethyl‐1‐piperidinyloxy (TEMPO) Sodium hypochlorite

Cited by 37 publications

References 12 publications

Direct Regiospecific and Highly Enantioselective Intermolecular α‐Allylic Alkylation of Aldehydes by a Combination of Transition‐Metal and Chiral Amine Catalysts

Direct Regiospecific and Highly Enantioselective Intermolecular α‐Allylic Alkylation of Aldehydes by a Combination of Transition‐Metal and Chiral Amine Catalysts

Nitroxides: Applications in Synthesis and in Polymer Chemistry

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

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