Baeyer-Villiger Oxidation of Ketones Using Molecular Oxygen and Benzaldehyde in the Absence of Metal Catalysts

Kaneda, Kiyotomi; Ueno, Shinji; Imanaka, Toshinobu; Shimotsuma, E.; Nishiyama, Yutaka; Ishii, Yasutaka

doi:10.1021/jo00090a001

Cited by 100 publications

(50 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast, Kaneda et al have recently shown that various cyclohexanone derivatives are efficiently oxidised to give lactones when using the combination of dioxygen and aldehydes in the absence of metal catalyst (tetrachloromethane, 40°C). [47] This observation suggests that peracid generated in situ from the autoxidation of the aldehyde with O 2 is not directly involved as a potential oxidising agent in our catalytic system and, consequently, that the metal complex plays an active role (see Discussion, below). However, under the same reaction conditions as used for the oxidation of secondary alcohols to ketones, the oxidation of primary benzylic alcohols afforded mixtures of starting material, aldehyde and the corresponding carboxylic acid, depending on the reaction time, as illustrated by p-nitrobenzyl alcohol (Entry 7).…”

Section: Catalytic Oxidation Of Alcoholsmentioning

confidence: 93%

Alcohol Oxidation by Dioxygen and Aldehydes Catalysed by Square-Planar Cobalt(III) Complexes of Disubstituted Oxamides and Related Ligands

Fernández¹,

Pedro²,

Roselló³

et al. 2001

Eur. J. Org. Chem.

View full text Add to dashboard Cite

The square-planar cobalt(III) complexes of o-phenylenebis(NЈ-methyloxamidate) (Me 2 opba) and related oxamate (Meopba) and bis(oxamate) (opba) ligands catalyse the selective oxidation, by dioxygen and pivalaldehyde, of a wide range of secondary alcohols to the corresponding ketones, in good yields and under mild conditions in acetonitrile at room temperature. Thus, the oxidation of the series of α-alkylbenzyl alcohols PhCH(OH)R (R = Me, Et, iPr, tBu) results in the exclusive formation of ketones as a product of C−H bond cleavage, and no C−C bond cleavage products are observed in any case. The modulation of catalytic activity by ligand substituents among this series of cobalt catalysts highlights the role of oxocobalt(IV) species as the putative inter-

show abstract

Section: Catalytic Oxidation Of Alcoholsmentioning

confidence: 93%

Alcohol Oxidation by Dioxygen and Aldehydes Catalysed by Square-Planar Cobalt(III) Complexes of Disubstituted Oxamides and Related Ligands

Fernández¹,

Pedro²,

Roselló³

et al. 2001

Eur. J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…The peracid can transfer an oxygen atom to a substrate, e.g., an olefin or a ketone, resulting in the formation of one equivalent of an epoxide or ester and acid as a coproduct in the absence of metal catalysts. [119][120][121][122] We found that both epoxidation and the Baeyer-Villiger oxidation using a system consisting of molecular oxygen and aldehydes were strongly dependent on the kinds of aldehydes used. For example, the Baeyer-Villiger oxidation of cyclohexanone with benzaldehyde smoothly occurred to give "-caprolactone, and benzoic acid was also formed as a coproduct, whereas aliphatic aldehydes such as isobutyraldehyde and isovaleraldehyde, which have high reactivities for epoxidation, showed lower yields of "-caprolactone than benzaldehyde.…”

mentioning

confidence: 99%

“…For example, the Baeyer-Villiger oxidation of cyclohexanone with benzaldehyde smoothly occurred to give "-caprolactone, and benzoic acid was also formed as a coproduct, whereas aliphatic aldehydes such as isobutyraldehyde and isovaleraldehyde, which have high reactivities for epoxidation, showed lower yields of "-caprolactone than benzaldehyde. 121 Hydrotalcites, Mg 10 Al 2 (OH) 24 CO 3 (Chart 3, type A), have been found to show high catalytic activity for the heterogeneous Baeyer-Villiger oxidation of various carbonyl compounds using a combination system of molecular oxygen and benzaldehyde. 123 A possible reaction mechanism of the BaeyerVilliger oxidation can be considered as follows: 124 (i) autoxidation of benzaldehyde with molecular oxygen affording per- …”

mentioning

confidence: 99%

Design of High-Performance Heterogeneous Metal Catalysts for Green and Sustainable Chemistry

Kaneda¹,

Ebitani²,

Mizugaki³

et al. 2006

Bulletin of the Chemical Society of Japan

Self Cite

142

View full text Add to dashboard Cite

This account reviews a novel approach to designing high-performance heterogeneous metal catalysts using hydroxyapatites, montmorillonites, and hydrotalcites as macroligands of active metal species for aerobic alcohol oxidations, carbon-carbon bond formations, and one-pot syntheses. The catalytic systems using the above heterogeneous catalysts offer significant benefits in achieving environmentally friendly organic syntheses aiming towards Green and Sustainable Chemistry. Furthermore, the present preparation method for the immobilization of metal species is strikingly simple and allows a strong protocol for creating various nanostructured and functionalized heterogeneous catalysts.Green and Sustainable Chemistry (GSC) is a revolutionary philosophy that aims to bring about a sustainable society by improvement of the safety and environmental aspects of chemical processes and reduction of the risks of chemical products to people and the environment.1 The emphasis is on eliminating waste at the source-primary pollution prevention-rather than finding incremental end-of-pipe solutions. This concept aims to solve the societal problems of the last century associated with the mass production and consumption of materials, and plays a prime role in providing a venous function in society, encouraging reuse and circulation of resources.One of the powerful solutions in the move toward GSC is the replacement of traditional synthetic methods using harmful stoichiometric reagents that produce vast amounts of waste with cleaner and simple catalytic alternatives with high atom efficiency 1a and low E-factors. 1b Catalytic chemistry, therefore, is of ever-increasing importance because catalysis is a key element in material transformations at atomic and molecular levels, which are an essential realm of chemistry and chemical processes.Our approach to GSC is to develop a highly functionalized heterogeneous metal catalyst based on the unique characteristics of natural layered inorganic materials such as hydroxyapatite, montmorillonite, and hydrotalcite, by using them as macroligands for metal species.2 We consider the above inorganic materials to be advanced nano-scaled catalyst supports allowing for the control of the location of catalytically active metal species, which can be found, for example, on the surface, among the layers, or in the interlayer space. Furthermore, these materials are capable of creating catalytically active metal species responsible for targeted organic transformations involving monomers, chain-like species or giant clusters. The creation of well-defined active metal sites on a solid surface, as characterized by X-ray absorption spectroscopy, not only opens up an avenue to materials that boost catalytic performance, but also aids in the understanding of the molecular basis of heterogeneous catalysis. Another advantage of these catalysts is the possibility of a one-pot synthesis based on a cooperative action by several immobilized active species on the solid surface as multifunctional catalysts. The target react...

show abstract

“…This view, [49] and with the fact that with benzaldehyde the reaction can proceed even in the absence of catalyst. [54] However, in all other systems reported above and based on more elaborate catalyst formulation, only cyclic ketones are reported to be oxidized in contrast with the known reactivity for an in situ produced peroxy acid. This observation and the fact that the system has been modified successfully to accomplish the Baeyer ± Villiger enantioselective transformation (see Section 5) seem to suggest that the metal may also be actively involved in the oxygen transfer step, although how is still unclear.…”

Section: Titanium Silicalite (Ts-1)mentioning

confidence: 91%

Transition Metal Catalysis in the Baeyer-Villiger Oxidation of Ketones

Strukul¹

1998

Angewandte Chemie International Edition

336

View full text Add to dashboard Cite

show abstract

Baeyer-Villiger Oxidation of Ketones Using Molecular Oxygen and Benzaldehyde in the Absence of Metal Catalysts

Cited by 100 publications

References 0 publications

Alcohol Oxidation by Dioxygen and Aldehydes Catalysed by Square-Planar Cobalt(III) Complexes of Disubstituted Oxamides and Related Ligands

Alcohol Oxidation by Dioxygen and Aldehydes Catalysed by Square-Planar Cobalt(III) Complexes of Disubstituted Oxamides and Related Ligands

Design of High-Performance Heterogeneous Metal Catalysts for Green and Sustainable Chemistry

Transition Metal Catalysis in the Baeyer-Villiger Oxidation of Ketones

Contact Info

Product

Resources

About