Azirine formation by decomposition of terminal vinyl azides

Isomura, Kazuaki; Okada, Michiyo; Taniguchi, Hiroshi

doi:10.1016/s0040-4039(01)88618-4

Cited by 42 publications

(24 citation statements)

References 11 publications

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“…More importantly, an unprecedented conversion of 2 c into NH aziridine 7 a, which is catalyzed by potassium phosphate (K 3 PO 4 ), was discovered. [14] These results demonstrate the usefulness of 2-azidoallyl alcohols as synthetic intermediates. Aziridines are important synthetic building blocks for the construction of complex nitrogen-containing compounds.…”

Section: Methodsmentioning

confidence: 65%

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

et al. 2014

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The hydroazidation of alkynes is the most straightforward pathway to synthetically useful vinyl azides. However, a general hydroazidation of alkynes remains elusive. Herein, a chemo- and regioselective transformation of ethynyl carbinols into vinyl azides is described. This reaction produces a wide variety of 2-azidoallyl alcohols with high efficiency and in good to excellent yields. These compounds constitute a new class of densely functionalized synthetic intermediates. Their synthetic potential has been demonstrated by further transformations into NH aziridines. The mechanistic aspects of the reaction will attract the attention of chemists working on alkyne chemistry and silver catalysis. The findings that are described in this paper represent significant advances in the regioselective hydroelementation of alkynes and open a new reaction manifold for exploitation.

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Section: Methodsmentioning

confidence: 65%

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

et al. 2014

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mentioning

confidence: 65%

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

Liu

Zhang

et al. 2014

Angewandte Chemie

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The hydroazidation of alkynes is the most straightforward pathway to synthetically useful vinyl azides. However, a general hydroazidation of alkynes remains elusive. Herein, a chemo-and regioselective transformation of ethynyl carbinols into vinyl azides is described. This reaction produces a wide variety of 2-azidoallyl alcohols with high efficiency and in good to excellent yields. These compounds constitute a new class of densely functionalized synthetic intermediates. Their synthetic potential has been demonstrated by further transformations into NH aziridines. The mechanistic aspects of the reaction will attract the attention of chemists working on alkyne chemistry and silver catalysis. The findings that are described in this paper represent significant advances in the regioselective hydroelementation of alkynes and open a new reaction manifold for exploitation.

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“…'l'he corresponding products -2,3-tlimetIiyl-5,6-tliphenylpyrazine (6), 2-methylintlole (4, R = CH3) and a-phenylpropionitrile (5, R = Cl13)were derived from the residue 2 (K = C113). In contrast, irradiation of the styryl isocyanate (1, K = C6H5) did not give tetraplienylpyrazine (7), 2-phenylindole and diphenylacetonitrile; however, 2,3,4,5-tetraphenylpyrrole (8) and 3-phenylisocarbostyril (9) were obtained.…”

Section: Kesitltsmentioning

confidence: 89%

Photo‐decarbonylation of β‐styryl isocyanates

Boyer

Mikol

1972

Journal of Heterocyclic Chem

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β‐Styryl isocyanate (1, R  H) and its β‐methyl‐ (1, R  CH3) and β‐phenyl‐ (1, R  C6H5) derivatives underwent both extensive polymerization and the loss of the elements of carbon monoxide upon irradiation at 254 nm in cyclohexane. The formation of 2,5‐diphenylpyrazine (3) and indole 4, (R  H) from 1, (R ‐ H) and 2,3‐dimethyl‐5,6‐diphenylpyrazine (6) and 2‐methylindole (4, R  CH3) from 1, (R  CH3) provided diagnostic evidence for styryl nitrene (2a) intermediates. The formation of both phenylacetonitrile (5, R  H) and α‐phenylpropio‐nitrile (5, R  CH3) was assigned to an initial rearrangement of the residue, C8H6(R)N̈: (2), into a ketenimine concerted with the elimination of carbon monoxide from 1. Isomerization then produced a nitrile. β3‐(β‐phenyl)styryl isocyanate (1, R  C6H5) gave no product requiring the intermediacy of a nitrene and/or an azirine. The formation of 2,3,4,5‐tetraphenylpyrrole (8) was assigned to a dimerization of the isocyanate concerted with or following the elimination of the elements of carbon monoxide and isocyanic acid, and the formation of 3‐phenylisocarbo‐styril (9) was assigned to a ring‐closure of the isocyanate in an excited triplet state. Each isocyanate gave stilbene and trace amounts of oxidative fragmentation into benzaldehyde and benzonitrile. Solvent participation produced benzylcyclohexane and bicyclohexyl. Two unidentified solids, C17H14N2O and C12H14N2O, were obtained from 1, (R  CH3).

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Azirine formation by decomposition of terminal vinyl azides

Cited by 42 publications

References 11 publications

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

Photo‐decarbonylation of β‐styryl isocyanates

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