Recent Advances in the Stereoselective Synthesis of Aziridines

Degennaro, Leonardo; Trinchera, Piera; Luisi, Renzo

doi:10.1021/cr400553c

Cited by 423 publications

(251 citation statements)

References 225 publications

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“…The most widely utilized methods for alkene aziridination involve the generation of metallonitrenes from iminoiodinane reagents. 4 These methods, unfortunately, produce stoichiometric haloarene byproducts, and there has consequently been significant interest in the use of alternate nitrene precursors for aziridination reactions. 5 Organic azides appear particularly attractive in this regard because they generate nitrenes by expelling dinitrogen as the sole stoichiometric byproduct.…”

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confidence: 99%

Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of Azidoformates

et al. 2016

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Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Here, we show that visible light activated transition metal complexes can be triplet sensitizers that selectively produce aziridines via the spin-selective photogeneration of triplet nitrenes from azidoformates. This approach enables the aziridination of a wide range of alkenes and the formal oxyamination of enol ethers using the alkene as the limiting reagent. Preparative scale aziridinations can be easily achieved in flow.

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Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of Azidoformates

et al. 2016

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“…[3] A particularly appealing strategy involves the catalytic transfer of nitrenes to alkenes, which has been extensively investigated and a wide range of metal-based catalysts have been reported. [4] These catalysts include many examples of iron-based complexes that are catalysts for aziridine synthesis by sulfilimine transfer.…”

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Styrene Aziridination by Iron(IV) Nitrides

et al. 2015

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Thermolysis of the iron(IV) nitride complex PhB(tBuIm)3Fe≡N with styrene leads to formation of the high spin iron(II) aziridino complex PhB(tBuIm)3Fe-N(CH2CHPh). Similar aziridination occurs with both electron-rich and electron-poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex PhB(tBuIm)3Fe-N(CH2CHPh) acts as a nitride synthon, reacting with electron poor styrenes to generate their corresponding aziridino complexes, i.e. aziridine cross-metathesis. Reaction of PhB(tBuIm)3Fe-N(CH2CHPh) with Me3SiCl releases the N-functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating PhB(tBuIm)3FeCl. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex PhB(MesIm)3Fe≡N reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.

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“…While the synthetic applications of aziridines have received much attention [11,25–29] there is little precedent of their opening with weak nucleophiles such as carboxylate anions [30]. However, we expected that the presence of the 2-methoxy substituent would facilitate the desired transformation.…”

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confidence: 99%

Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides

Huck

González

Cuesta

et al. 2016

Beilstein J. Org. Chem.

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SummaryA sequential three-component process is described, starting from 3-arylmethylene-2,5-piperazinediones and involving a one-pot sequence of reactions achieving regioselective opening of the 2,5-diketopiperazine ring and diastereoselective generation of an aziridine ring. This method allows the preparation of N-unprotected, trisubstituted aziridines bearing a peptide side chain under mild conditions. Their transformation into β-trifluoroacetamido-α-ketoamide and α,β-diketoamide frameworks was also achieved in a single step.

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Recent Advances in the Stereoselective Synthesis of Aziridines

Cited by 423 publications

References 225 publications

Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of Azidoformates

Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of Azidoformates

Styrene Aziridination by Iron(IV) Nitrides

Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides

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