Vinylphosphonate Formation via a Novel Cyclization−Vinyl Radical Trapping Sequence

Jiao, Xiaojin; Bentrude, Wesley G.

doi:10.1021/ja984460s

Cited by 43 publications

(27 citation statements)

References 12 publications

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“…[19] This strategy therefore can be applied to the synthesis of pharmaceuticals and bioactive natural products in astep-economic way. T EMPO [21] and P(OEt) 3 [22] could prevent the reactiont oo ccur and the alkylated TEMPO product (15)a nd vinylphosphonate (16)c ould be observed by GCMS, suggesting that this reactionm ight involve alkyl radicals and vinyl radicals [Eq. Te rminala lkylated phenylacetylene (12), acetophenone (13), and the vinyl ester (14) were tested and eliminated from consideration as the reaction intermediates [Eq.…”

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confidence: 99%

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Zhu

et al. 2017

Chemistry A European J

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An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C-C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.

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confidence: 99%

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Zhu

et al. 2017

Chemistry A European J

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“…[12] Combining the above information, we hypothesized that a-vinyl carbon radical/sulfonyl radical cross-coupling might be the key step in the transformation. In addition, radical trapping experiments were also performed (Scheme 3).…”

Section: Angewandte Chemiementioning

confidence: 98%

Markovnikov‐Selective Radical Addition of S‐Nucleophiles to Terminal Alkynes through a Photoredox Process

Wang

Chiang

et al. 2016

Angewandte Chemie

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Direct radical additions to terminal alkynes have been widely employed in organic synthesis, providing credible access to the anti-Markovnikov products. Because of the Kharasch effect, regioselective control for the formation of Markovnikov products still remains a great challenge. Herein, we develop a transition-metal-free, visible light-mediated radical addition of S-nucleophiles to terminal alkynes, furnishing a wide array of a-substituted vinyl sulfones with exclusive Markovnikov regioselectivity. Mechanistic investigations demonstrated that radical/radical cross-coupling might be the key step in this transformation. This radical Markovnikov addition protocol also provides an opportunity to facilitate the synthesis of other valuable a-substituted vinyl compounds.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.Scheme 3. Radical trapping experiments.Scheme 4. Operando IR experiments. Kinetic profiles for eosin Y (1 mol %), K 2 CO 3 (0.3 mmol) in DMF (4.0 mL) under different conditions: a) 1 a (0.3 mmol), under visible light; b) 2 a (0.6 mmol), under visible light; c) 2 a (0.6 mmol), addition of 1 a (0.3 mmol) after 1 h without visible light; d) 2 a (0.6 mmol), addition of 1 a (0.3 mmol) after 1 h under visible light. Scheme 5. Tentative mechanism. Angewandte Chemie Communications 597

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“…[10] Next, kinetic isotope effect (KIE) experimentsw ere performed. First, at rapping experiment was conducted to explore the existence of intermediates (Scheme 3a).…”

Section: Entriesmentioning

confidence: 99%

Electrochemical Oxidative C(sp³)−H/N−H Cross‐Coupling for N‐Mannich Bases with Hydrogen Evolution

Wang

Yang

et al. 2019

ChemSusChem

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N-Mannich bases are an important structurei nv arious functional molecules. An ew protocol to synthesize N-Mannich bases was established throughe lectrochemical external-oxidant-free C(sp 3 )ÀH/NÀHc ross-coupling with hydrogen evolution. Various N-methylanilines were explored in this transformation. Moreover,s imple amides, heteroatom-containing amides, and succinimidesw ere well tolerated in moderate-to-good yields. In addition, the electrochemical dehydrogenative C(sp 3 )ÀH/NÀHc ross-couplingc ould be scaled up to 5mmol. By using triethylp hosphite as trapping agent,t he phosphorylation product wasd etected. At the same time, kinetic isotope effect experiments showedt hat the cleavageo ft he CÀHb ond is the rate-limiting step.

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Vinylphosphonate Formation via a Novel Cyclization−Vinyl Radical Trapping Sequence

Cited by 43 publications

References 12 publications

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Markovnikov‐Selective Radical Addition of S‐Nucleophiles to Terminal Alkynes through a Photoredox Process

Electrochemical Oxidative C(sp³)−H/N−H Cross‐Coupling for N‐Mannich Bases with Hydrogen Evolution

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Vinylphosphonate Formation via a Novel Cyclization−Vinyl Radical Trapping Sequence

Cited by 43 publications

References 12 publications

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Iron‐Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

Markovnikov‐Selective Radical Addition of S‐Nucleophiles to Terminal Alkynes through a Photoredox Process

Electrochemical Oxidative C(sp3)−H/N−H Cross‐Coupling for N‐Mannich Bases with Hydrogen Evolution

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Electrochemical Oxidative C(sp³)−H/N−H Cross‐Coupling for N‐Mannich Bases with Hydrogen Evolution