29392-97-0Relevant articles and documents
Mueller et al.
, p. 1479 (1970)
Hypervalent iodine-mediated aziridination of alkenes: Mechanistic insights and requirements for catalysis
Richardson, Robert D.,Desaize, Magalie,Wirth, Thomas
, p. 6745 - 6754 (2008/03/14)
By detailed study of the possible side reactions in the previously reported aziridination of alkenes with N-aminoheterocycles mediated by hypervalent iodine reagents, the requirements to make this reaction catalytic in iodoarene have been determined. The reaction requires an oxidant that will oxidise iodoarenes but that does not oxidise alkenes, but it is possible that no such oxidant actually exists! A method in which the hypervalent iodine reagent can be recycled without the need for reisolation is possible. Further study into the mechanism of this reaction gives tentative evidence that the reaction proceeds through formation of an aminoiodane that reacts directly with the alkene, contrary to previous literature reports in which an acetoxyamine intermediate is suggested. The temperature effect of this reaction is remarkable.
Mild thermal route to phthalimidonitrene and its reaction with activated benzenes to give 2H- and 3H-azepines; X-ray crystal structure analysis of an isolable 2H-azepine
Jones, David W.,Thornton-Pett, Mark
, p. 809 - 816 (2007/10/02)
At 80 deg C 1a-acetyl-1-phthalimido-1a,6b-dihydrobenzofuroazirine 1 (X = Ac) transfers phthalimidonitrene to a series of traps: Me2SO, 2-methoxynaphthalene, indene, methyl methacrylate, methyl crotonate, mesityl oxide, cis- and trans-stilbene and cyclohexene.Oxidation of N-aminophthalimide with lead tetraacetate in the presence of these traps gives the same major products (ref. 2a).With 1,3-dimethoxybenzenes, the reagent 1 (X = Ac) provides 2H- and 3H-azepines e,g. 25a and 24a as the major products with N-phthalimidoanilines e.g. 18 formed to a lesser extent.On the other hand Pb(OAc)4 oxidation of N-aminophthalimide in the presence of 1,3-dimethoxybenzenes gives N-phthalimidoanilines and no detectable 2H- or 3H-azepines.Small quantities of acetic or benzoic acid present during the dissociation of 1 (X = Ac) in the presence of 1,3-dimethoxybenzenes cause marked increases in the formation of N-phthalimidoanilines compared with azepines.The unusually stable and isolable 2H-azepines 25 rearrange to 3H-azepines 24 only on heating and 5,7-dimethoxy-3-methyl-2-phthalimido-2H-azepine 25d is characterised by X-ray crystal structure analysis.
