Self-terminating, oxidative radical cyclizations of medium-sized cycloalkynones with inorganic and organic oxygen-centered radicals of type XO˙: the reaction pathway depends on the nature of X

Wille, Uta; Jargstorff, Christian

doi:10.1039/b201672a

Cited by 16 publications

(13 citation statements)

References 30 publications

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“…Because of the instability of 7aϪd, these compounds were prepared in situ and used immediately, as described in the literature. [15,38] The nitroxyl radicals 13aϪd were generated from the corresponding hydroxylamines 12 [39,40] by one-electron oxidation (see below). Reaction analysis was accomplished by GC and GC-MS, and the products were identified by comparison both of GC retention times and of NMR spectra with those of authentic samples and with literature data.…”

Section: Resultsmentioning

confidence: 99%

“…They were prepared in situ and used immediately (see below) in analogy to a procedure described in the literature. [15,38] The radical precursors 10a and 10g were synthesized according to ref. [15] Product identification was performed by comparison both of GC retention times and of NMR spectra with those of authentic samples and literature data.…”

Section: Methodsmentioning

confidence: 99%

“…[15,38] The radical precursors 10a and 10g were synthesized according to ref. [15] Product identification was performed by comparison both of GC retention times and of NMR spectra with those of authentic samples and literature data. [9] …”

Section: Methodsmentioning

confidence: 99%

“…We have shown that the termination of this cyclization cas-cade is kinetically controlled and determined by the ease of the final homolytic cleavage of the OϪX bond. [15] Encouraged in particular by the finding that the highly unstable acyloxyl radicals RC(O)O…”

Section: Introductionmentioning

confidence: 98%

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Self‐Terminating Radical Oxygenations: Probing of the Scope of the Concept by Use of Various Organic O‐Centered Radicals

Jargstorff

Wille

2003

Eur J Org Chem

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Addition of various organic O‐centered radicals XO• {i.e. (alkoxycarbonyl)oxyl radicals, ROC(O)O•, [(alkoxycarbonyl)acyl]oxyl radicals, ROC(O)C(O)O•, (carbamoyl)oxyl radicals, R2NC(O)O•, alkoxyl radicals, RO•, and nitroxyl radicals, R2NO•} to alkynes initiates an oxidative radical cyclization cascade, which is terminated by release of a C‐ or N‐centered radical X•. This finding clearly highlights the generality of the recently discovered concept of self‐terminating radical oxygenations, through which C≡C triple bonds may be converted into carbonyl groups under very mild reaction conditions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Self‐Terminating Radical Oxygenations: Probing of the Scope of the Concept by Use of Various Organic O‐Centered Radicals

Jargstorff

Wille

2003

Eur J Org Chem

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“…In go-Scheme 1. Preparation of N-methoxythiazole-2(3H)-thiones; reagents and conditions: (a) NEt 4 OH, MeOH, then freeze-drying for 3b; (b) NBu 4 OH, MeOH, then freeze-drying; synthesis of 4b-7b; [25] (c) TsOCH 3 , DMF, 20°C…”

Section: N-hydroxythiazole-2(3h)-thiones 3a-7amentioning

confidence: 99%

4‐ and 4,5‐Substituted N‐Methoxythiazole‐2(3H)‐thiones – Preparation,UV/Vis Spectra, and Assignment of Electronic Transitions in Comparison to N‐Methoxypyridine‐2(1H)‐thione Using Time‐Dependent Density Functional Theory Calculations

Hartung¹,

Špehar²,

Svoboda³

et al. 2005

Eur J Org Chem

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Keywords:Alkoxyl radical precursor / Pyridinethione / Thiazolethione/ Thiocarbonyl chromophore/ Time-dependent density functional theoryExperimentally observed absorptions in UV/Vis spectra of N--thione, and selected N-hydroxy derivatives thereof have been assigned to πǞπ*-type transitions as dominating character, using the results from ab initio calculations [time-dependent density functional theory (TD)RI-BLYP/ TZVPP]. Theory further predicts that electronic excitations in N-methoxythiazole-2(3H)-thiones on one side and N-methoxypyridine-2(1H)-thione on the other side differ significantly with respect to character and statistical weight of contributing transitions. These effects originate predominantly from contributions of the endocyclic sulfur atom onto orbital energies and shapes in thiazole-2(3H)-thiones, and may be

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4-(4-Chlorophenyl)-3-hydroxy-2(3H)thiazolethione

Hartung

2004

Encyclopedia of Reagents for Organic Synthesis

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Self-terminating, oxidative radical cyclizations of medium-sized cycloalkynones with inorganic and organic oxygen-centered radicals of type XO˙: the reaction pathway depends on the nature of X

Cited by 16 publications

References 30 publications

Self‐Terminating Radical Oxygenations: Probing of the Scope of the Concept by Use of Various Organic O‐Centered Radicals

Self‐Terminating Radical Oxygenations: Probing of the Scope of the Concept by Use of Various Organic O‐Centered Radicals

4‐ and 4,5‐Substituted N‐Methoxythiazole‐2(3H)‐thiones – Preparation,UV/Vis Spectra, and Assignment of Electronic Transitions in Comparison to N‐Methoxypyridine‐2(1H)‐thione Using Time‐Dependent Density Functional Theory Calculations

4-(4-Chlorophenyl)-3-hydroxy-2(3H)thiazolethione

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