Cobalt–Salen Complex-Catalyzed Oxidative Generation of Alkyl Radicals from Aldehydes for the Preparation of Hydroperoxides

Watanabe, Eiichi; Kaiho, Atsushi; Kusama, Hiroyuki; Iwasawa, Nobuharu

doi:10.1021/ja406028c

Cited by 42 publications

(17 citation statements)

References 61 publications

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“…The dried (Na 2 SO 4 ) organic layer was concentrated, and the residue was purified through a short plug of silica (10% EA/hexane) to furnish 2-hydroperoxy-2-methylpropyl)benzene [1944-83-8] as a colorless oil (0.41 g, 98%), which displayed spectral data matching literature reports. 78 R f = 0.35 (10% EA/hex).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

et al. 2015

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Although transfer of electrophilic alkoxyl (“RO+”) from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O–O bond.

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Section: Methodsmentioning

confidence: 99%

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

et al. 2015

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“…[3] In addition, it was demonstrated that -substituted pyruvic acid derivatives undergo oxidative decarbonylation in the presence of sodium perborate tetrahydrate to yield the corresponding acetic acid derivatives. [5] Recently, Maiti et al disclosed a non-oxidative palladium-catalyzed deformylation protocol for aromatic aldehydes. [5] Recently, Maiti et al disclosed a non-oxidative palladium-catalyzed deformylation protocol for aromatic aldehydes.…”

Section: Introductionmentioning

confidence: 99%

“…[4] Iwasawa and co-workers reported on the catalytic generation of alkyl radicals from aldehydes using a cobalt-salen complex with H 2 O 2 . [5] Recently, Maiti et al disclosed a non-oxidative palladium-catalyzed deformylation protocol for aromatic aldehydes. [6,7] Schöning and co-workers reported on the conversion of aldehydes to the corresponding N-alkoxyamines by using stable nitroxide radicals (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

TEMPO‐Mediated Oxidative Deformylation of Aldehydes: Applications in the Synthesis of Polyketide Fragments

et al. 2017

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A TEMPO‐mediated oxidative deformylation of aldehydes is reported that yields the TEMPO adducts, which can be further oxidized to the corresponding ketones. The focus of this work was on the optimization of a synthetic protocol for use in natural product synthesis, specifically for the preparation of chiral backbones with 1,2‐oxo functionalization found in polyketide antibiotics. In addition, the oxidative deformylation was combined with the oxidation of the alcohol to the precursor aldehyde in a one‐pot protocol.

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“…Organicp eroxides are useful functional groups in organic synthesis. [14,15] However,c urrent hydroperoxyarylation methods requiree ither an oxygen atmosphere [7a] or slow addition of the aryl hydrazine. [7b] The hydroperoxyarylation of mono-substituted olefins is problematic,w hich is often hampered by moderate yields.…”

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confidence: 99%

Remazol‐Catalyzed Hydroperoxyarylation of Styrenes

Chen

Liu

Lin

et al. 2015

Chemistry An Asian Journal

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A mild photocatalytic hydroperoxyarylation of styrenes has been developed, in which a novel photocatalyst, remazol brilliant blue R (RBBR), is employed at low catalytic loading (1 mol %). The operationally easy procedure uses air as the dioxygen source. Simple mono-substituted styrenes react with aryl hydrazines in moderate-to-good yields. RBBR is proposed to act as a photosensitizer for the generation of singlet oxygen.

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Cobalt–Salen Complex-Catalyzed Oxidative Generation of Alkyl Radicals from Aldehydes for the Preparation of Hydroperoxides

Cited by 42 publications

References 61 publications

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

TEMPO‐Mediated Oxidative Deformylation of Aldehydes: Applications in the Synthesis of Polyketide Fragments

Remazol‐Catalyzed Hydroperoxyarylation of Styrenes

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