Metal‐Free Regioselective Chloroazidation of Internal Alkynes

Huang, Bin; Liffert, Raphael; Linden, Anthony; Gademann, Karl

doi:10.1002/chem.201805320

Cited by 6 publications

(4 citation statements)

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“…Propargylic benzoate 9d (60 mg, 0.20 mmol) and NBS (75 mg, 0.43 mmol) were refluxed using an oil bath in CH 3 CN/H 2 O (3.0 mL each) for 30 min at 55 °C, and α,α-dibromoketone 12d (87 mg, 0.18 mmol, 92%) was isolated as a yellow color oil.…”

Section: Experimental Sectionmentioning

confidence: 99%

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Tunable Lewis Basicity and Nucleophilicity of Water against α,α-Dihalo-β-acetoxyketones for the Selective Synthesis of α-Haloenones and 1,2-Diketones

Sadhukhan

Baire

2022

J. Org. Chem.

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The discovery and systematic study of tunable yet competitive nucleophilicity and Lewis basicity of water against novel building blocks α,α-dihalo-β-acetoxyketones (possessing a tertiary acetate) have been reported. This distinct reactivity resulted in the formation of two competitive and different products 1,2-diketones and α-haloenones from a common intermediate α,α-dihaloβ-acetoxyketones through the nucleophilicity and Lewis basicity of water, respectively. A systematic study to understand the effect of temperature and amount of water on the product distribution revealed that a lower temperature in combination with a higher amount of water shows a high preference for 1,2-diketones over α-haloenones. Measuring the dielectric constant (permittivity, ε) of various reaction media at various temperatures and a correlation with the experimental observations suggested that the reaction media with a higher dielectric constant exhibit the nucleophilic character and hence show a preference for 1,2-diketones over αhaloenones.

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Section: Experimental Sectionmentioning

confidence: 99%

“…Propargylic acetate 9i (70 mg, 0.34 mmol) and NBS (134 mg, 0.76 mmol) were refluxed using an oil bath (6.5 mL of CH 3 CN and 0.07 mL of H 2 O) for 6 h at 100 °C, and α-bromoenone 11i (77 mg, 0.32 mmol, 95%) was isolated as a colorless oil, along with 1,2-diketone 10i (3 mg, 0.012 mmol, 2%).…”

Section: Experimental Sectionmentioning

confidence: 99%

Tunable Lewis Basicity and Nucleophilicity of Water against α,α-Dihalo-β-acetoxyketones for the Selective Synthesis of α-Haloenones and 1,2-Diketones

Sadhukhan

Baire

2022

J. Org. Chem.

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“…In the presence of 1,3‐dichloro‐5,5‐dimethylhydantoin (DCDMH), internal alkyne reacts with trimethylsilyl azide (TMSN 3 ) to give the corresponding chloroazide alkene. In addition, heating in toluene at 90°C for 12 h yielded a single isomer of chloro‐2 H ‐azirine (Scheme 90) [114].…”

Section: Radical Addition and Cyclization Of Alkynesmentioning

confidence: 99%

Synthesis of various functionalized 2H‐azirines: An updated library

Majee

2021

Journal of Heterocyclic Chem

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In the current extensive review, we pay special attention to the progress in the synthesis of 2H‐azirine. Content is organized by several main approaches for the synthesis of 2H‐azirines such as‐ Neber rearrangement, decomposition of vinyl azides, oxidative cyclization of enamines, ring contraction of isoxazoles or oxazaphospholes, radical addition/cyclization of alkynes, Swern oxidation or elimination reactions of aziridine derivatives, catalytic decomposition of α‐oximino diazo compounds, addition of silyldibromomethyllithium compounds to nitriles, addition of carbenes to nitriles and via azirine‐azirine transformations. Some of these approaches open up access to new 2H‐azirine derivatives and make the already established compounds more convenient. A description of these methods and the progress of using well‐known reactions leading to the aziridine system are presented in this section. This review surveys the progress of various functionalized 2H‐azirine formation reactions from the exploration period to the present.

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“…Organic azides (RN 3 ) have an ever‐expanding inventory of reactivity. They are widely tapped in organic synthesis, because of they have great stability at room temperature and are a resource to easily introduce versatility of the nitrogen substituents in the products . Furthermore, there exists an increasing interest to use them as protein labeling and in click chemistry .…”

Section: Introductionmentioning

confidence: 99%

Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations

Algarra

Soto

2020

ChemPhysChem

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This work studies the photochemical and thermal decompositions of azidoacetonitrile (N3CH2CN) from both the experimental and theoretical points of view. The data of the photochemical experiments are taken from the literature, while the thermal decomposition have been carried out by us. In addition, we have performed ab initio calculations of the multiconfigurational type [complete active space self‐consistent field (CASSCF) and the multistate multireference perturbation theory (MS‐CASPT2)]. It is found that the first step of both type of decompositions is N2 elimination and formation of closed shell singlet nitrene. Afterwards, the nitrene tends to rapidly rearrange into formimidoyl cyanide (HNCHCN). As both reactions progress, the imine isomerizes into formimidoyl isocyanide (HNCHNC). The photoisomerization of the imine takes places thorough a conical intersection, while the same reaction on the ground electronic state occurs via a conventional transition state. The last step of the global reaction is decomposition of the imines into HCN and CNH. In photochemical conditions, the conjunction of the imines and its dissociation products (HCN and CNH) yields adenine

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Metal‐Free Regioselective Chloroazidation of Internal Alkynes

Cited by 6 publications

References 50 publications

Tunable Lewis Basicity and Nucleophilicity of Water against α,α-Dihalo-β-acetoxyketones for the Selective Synthesis of α-Haloenones and 1,2-Diketones

Tunable Lewis Basicity and Nucleophilicity of Water against α,α-Dihalo-β-acetoxyketones for the Selective Synthesis of α-Haloenones and 1,2-Diketones

Synthesis of various functionalized 2H‐azirines: An updated library

Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations

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