286. The fission of non-enolisable ketones by potassium tert.-butoxide

Swan, G. A.

doi:10.1039/jr9480001408

Cited by 39 publications

(52 citation statements)

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“…On the basis of the above results and previous reports, we proposed a plausible reaction mechanism for this transformation detailed in Scheme . This transformation pathway is initiated by aminocupration of 2-alkynyl aniline to afford the organocopper(II) intermediate A , which would be further oxidized to intermediate B in the presence of oxygen.…”

Section: Resultssupporting

confidence: 60%

Copper-Catalyzed Synthesis of Substituted Quinazolines from Benzonitriles and 2-Ethynylanilines via Carbon–Carbon Bond Cleavage Using Molecular Oxygen

Wang

Huang

et al. 2018

J. Org. Chem.

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A copper-catalyzed process for the synthesis of substituted quinazolines from benzonitriles and 2-ethynylanilines using molecular oxygen (O) as sole oxidant is described. The mild catalytic system enabled the effective cleavage of the C-C triple bond and construction of new C-N and C-C bonds in one operation. Furthermore, the compound N, N-dimethyl-4-(2-(4-(trifluoromethyl)phenyl)quinazolin-4-yl)aniline (3dj) exhibited obvious aggregation-induced emission phenomenon, and the fluorescence quantum yield (Φ) and lifetime (τ) were measured to be 45.5% and 5.8 ns in thin films state, respectively.

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Section: Resultssupporting

confidence: 60%

Copper-Catalyzed Synthesis of Substituted Quinazolines from Benzonitriles and 2-Ethynylanilines via Carbon–Carbon Bond Cleavage Using Molecular Oxygen

Wang

Huang

et al. 2018

J. Org. Chem.

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“…Further analysis of the starting material showed trace amounts of 33 present in the commercially supplied triphenylmethanol 32 . Background formation of benzophenone 33 , in trace amounts from heterolytic fragmentation of similar tertiary alkoxides with expulsion of a phenyl anion, is also precedented [ 25 , 26 ].…”

Section: Resultsmentioning

confidence: 99%

KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4

et al. 2018

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The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.

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“…The present traceless linker is based on the cleavage of non-enolizable ketones, see Reaction 1, by treatment with the heterogeneous mixture formed by adding small amounts of water to potassium t-butoxide (typical mol ratio 3 : 10) in an ethereal solvent such as 1,2-dimethoxyethane or tetrahydrofuran (THF) : the so-called butoxide-water reagent (BWR). [34][35][36] It is believed that in these reactions initially the carbonyl group of the ketone is attacked by the hydroxide anion and then the tetrahedral intermediate formed is deprotonated by t-butoxide to give dianion 1. 35 The latter cleaves to give a carboxylate anion and a carbanion: Reaction 2.…”

Section: Resultsmentioning

confidence: 99%

Polymer-supported syntheses of thiophene-containing compounds using a new type of traceless linker

Ben-Haida

Hodge

2012

Org. Biomol. Chem.

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A new type of traceless linker is described for use in polymer-supported (PS) syntheses of thiophene-containing compounds. It is based on the cleavage of PS aryl 2-thienyl ketones by a mixture of potassium t-butoxide and water (typical mol ratio 10:3) in an ethereal solvent. Cleavage occurs to give the soluble thiophene-containing product. The method is used to prepare a range of eight thiophene-containing compounds including a terthiophene and a dialkylquaterthiophene. PS unsymmetrical diaryl ketones incorporating, for example, ortho-methoxyphenyl or pyrrole moieties could also serve as traceless linkers.

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286. The fission of non-enolisable ketones by potassium tert.-butoxide

Cited by 39 publications

References 0 publications

Copper-Catalyzed Synthesis of Substituted Quinazolines from Benzonitriles and 2-Ethynylanilines via Carbon–Carbon Bond Cleavage Using Molecular Oxygen

Copper-Catalyzed Synthesis of Substituted Quinazolines from Benzonitriles and 2-Ethynylanilines via Carbon–Carbon Bond Cleavage Using Molecular Oxygen

KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4

Polymer-supported syntheses of thiophene-containing compounds using a new type of traceless linker

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