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Oxidation of secondary alcohols to ketones

About: Oxidation of secondary alcohols to ketones is a research topic. Over the lifetime, 61 publications have been published within this topic receiving 1887 citations.


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Journal ArticleDOI
TL;DR: Recent studies on catalytic aerobic oxidations with photoactivated nitrosyl ruthenium-salen complexes, including asymmetric oxidation of secondary alcohols to ketones (kinetic resolution), enantioselective oxidative coupling of 2-naphthols to binaphthols and oxygen-radical bicyclization of 2,2'-dihydroxystilbene, and asymmetric desymmetrization of meso-diols to lactols.
Abstract: Selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most fundamental reactions in organic synthesis. Traditional methods for this transformation generally rely on stoichiometric amount of oxidants represented by Cr(VI) or DMSO reagents, though their synthetic utility is encumbered by unpleasant waste materials. From ecological and atom-economic viewpoints, catalytic aerobic oxidation is much more advantageous because molecular oxygen is ubiquitous and the byproduct is basically non-toxic water or hydrogen peroxide. On the other hand, phenol derivatives undergo oxidative coupling, forming CC or CO bond, through radical intermediates coupled with an electron-transfer process. Molecular oxygen is also well known to serve as electron acceptor in this reaction. Thus, a variety of transition metal complexes have so far been examined for aerobic oxidations of alcohols and phenols, and high catalytic activities have been achieved in some cases. However, stereo- and chemo-selective aerobic oxidations are still limited in number and are of current interest. Presented in this paper is our recent studies on catalytic aerobic oxidations with photoactivated nitrosyl ruthenium-salen complexes, including asymmetric oxidation of secondary alcohols to ketones (kinetic resolution), enantioselective oxidative coupling of 2-naphthols to binaphthols and oxygen-radical bicyclization of 2,2′-dihydroxystilbene, chemoselective oxidation of primary alcohols to aldehydes and diols to lactols, and asymmetric desymmetrization of meso-diols to lactols. © 2004 The Japan Chemical Journal Forum and John Wiley & Sons, Inc. Chem Rec 4: 96–109; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20001

54 citations

Journal ArticleDOI
TL;DR: These findings are rationalized by proposing models for the diastereomeric intermediates between (R)-[and (S)]-1-phenylethanol and the catalyst Fmoc-TOAC-L-(alphaMe)Val-NHiPr, based on the X-ray diffraction structure of the latter.
Abstract: The oxidation of secondary alcohols to ketones by use of aliphatic nitroxyl radicals, such as TEMPO, as catalysts is a well known reaction which involves in the oxidation path an N-oxoammonium salt originated from the corresponding nitroxyl radical. Complex chiral nitroxyl molecules have been used as catalysts to induce enantioselective oxidation reactions [1].

52 citations

Journal ArticleDOI
TL;DR: In this paper, a new process for the oxidation of secondary alcohols to ketones using peroxyacetic acid in the presence of a catalytic amount of 2,4-dimethylpentane-2, 4-diol cyclic chromate was described.

46 citations

Journal ArticleDOI
TL;DR: The chiral ligand (-)-sparteine and PdCl(2) catalyze the enantioselective oxidation of secondary alcohols to ketones and thus effect a kinetic resolution, which shows that these C(2)-symmetric counterparts are inferior ligands in this stereoablative reaction.
Abstract: The chiral ligand (−)-sparteine and PdCl_2 catalyze the enantioselective oxidation of secondary alcohols to ketones and thus effect a kinetic resolution. The structural features of sparteine that led to the selectivity observed in the reaction were not clear. Substitution experiments with pyridine derivatives and structural studies of the complexes generated were carried out on (sparteine)PdCl2 and indicated that the C1 symmetry of (−)-sparteine is essential to the location of substitution at the metal center. Palladium alkoxides were synthesized from secondary alcohols that are relevant steric models for the kinetic resolution. The solid-state structures of the alkoxides also confirmed the results from the pyridine derivative substitution studies. A model for enantioinduction was developed with C1 symmetry and Cl− as key features. Further studies of the diastereomers of (−)-sparteine, (−)-α-iso- and (+)-β-isosparteine, in the kinetic resolution showed that these C_2-symmetric counterparts are inferior ligands in this stereoablative reaction

43 citations

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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
20201
20191
20173
20152
20142
20131