29392-97-0Relevant academic research and scientific papers
Thermal rearrangement of 2,3-diaryl-1-phthalimidoaziridines
Pankova, Alena S.,Sorokina, Mariia V.,Kuznetsov, Mikhail A.
supporting information, p. 5381 - 5385 (2015/09/15)
2,3-Diaryl-1-phthalimidoaziridines and 2,3-diaryl-1-phthalimidoaziridine-2-carbonitriles were found to readily undergo thermal rearrangement into imines via 1,2-migration of the phthalimido group and accompanying C-C bond cleavage. Isomerization proceeds regioselectively with preferable migration to the electron-deficient carbon atom. Interestingly, this reaction was found to predominate even in the presence of dipolarophiles.
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.
Aryl iodide mediated aziridination of alkenes
Li, Jiayin,Chan, Philip Wai Hong,Che, Chi-Ming
, p. 5801 - 5804 (2007/10/03)
(Chemical Equation Presented) Aryl iodide mediated aziridination of a variety of alkenes with N-aminophthalimide under mild conditions (m-CPBA, K 2CO3, CH2Cl2, 25°C) was achieved in moderate to good yields (up to 94%). By recovering the aryl iodide, a recyclable system is developed with product yield over 79% attained for the aziridination of trans-1,2-diphenylethylene.
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.
Lithium Aluminum Hydride Reduction of N-Aziridinylimines to Hydrocarbons
Leone, Christina L.,Chamberlin, A. Richard
, p. 1691 - 1694 (2007/10/02)
The hydride reduction of ketone and aldehyde N-aziridinylimines is reported.Unlike most other hydrazone reductions, the reaction proceeds at room temperature under non-acidic conditions, providing an unusually mild carbonyl-to-methylene conversion.
Thermolysis of 7-(Acylamino)-7-azabenzonorbornadienes and 1-(Acylamino)aziridines. Generation and Trapping of Monosubstituted Azamines
Carpino, Louis A.,Padykula, Robert E.,Lee, Sung-Nung,Han, Grace Y.,Kirkley, Robert K.
, p. 6047 - 6053 (2007/10/02)
The thermolysis of 7-carbonyl>amino>- and 7-(benzoylamino)-7-azabenzonorbornadienes (2a and 2 b) in various solvents has been studied.In the absence of an olefinic trapping agent the major products other than naphthalene are the corresponding hydrazides 6a,b.In cyclohexene as solvent, the aziridines 7a,b are formed, suggesting that the azamine 3 is ejected and captured by the olefin.For the olefin cis-4-methyl-2-pentene the reaction occurs with greater than 95percent stereoselectivity in further agreement with a labile azamine intermediate.Thisrepresents the first demonstration that a monosubstituted azamine has independent existence and reacts with olefin faster than it undergoes 1,2-hydrogen shift.Synthesis of the related 7-phthalimido-7-azabenzonorbornadiene (17) was achieved via rearrangement of the corresponding isophthalimide derivative 18, which could be obtained by reaction of phthaloyl chloride with hydrazine 1.Thermolysis of 17 caused fragmentation to naphthalene and phthaloylazamine 13 as shown by trapping of the latter.This reaction represents a new thermal source of transient species 13.For synthetic purposes more practical intermediates for the generation of 3 are the aziridines 21 and 22.The cis analogues (23) of 21 proved to be relatively stable thermally.A new route is presented for the synthesis of 1-amino-cis-2,3-diphenylaziridine.
