64300-27-2Relevant academic research and scientific papers
Enantiopure trans -3-arylaziridine-2-carboxamides: Preparation by bacterial hydrolysis and ring-openings toward enantiopure, unnatural D -α-amino acids
Moran-Ramallal, Roberto,Liz, Ramon,Gotor, Vicente
supporting information; experimental part, p. 6614 - 6624 (2010/11/17)
Several racemic trans-3-arylaziridine-2-carboxamides were prepared and then resolved by Rhodococcus rhodochrous IFO 15564-catalyzed hydrolysis. The resulting enantiopure (2R,3S)-3-arylaziridine-2-carboxamides are adequate substrates to undergo fully stereoselective nucleophilic ring-openings at the C-3 ring position to finally yield enantiopure, unnatural d-α- aminocarboxylic acids. Experimental evidence is provided that suggests the fate of the (2S,3R)-3-arylaziridine-2-carboxylic acids concomitantly formed during the resolution processes. In this context, the similar bacterial resolution of racemic 1-arylaziridine-2-carboxamides and -carbonitriles, previously investigated by our research group, has been partially re-examined.
The synthesis of alkyl aryl nitriles from N-(1-arylalkylidene)-cyanomethylamines. Part 2. Mechanism
Perosa, Alvise,Selva, Maurizio,Tundo, Pietro
, p. 1033 - 1037 (2007/10/03)
The mechanism of the rearrangement of N-(1-arylalkylidene)cyanomethylamines ArC(=NCH2CN)R 1 to the corresponding nitriles ArCH(CN)R2 (in DMF, at 150°C, with K2CO3) is described. Reaction 1 → 2 was investigated for different types of imine 1, and it was found that with a leaving group other than CN- the reaction does not proceed to yield the nitrile, whereas imines such as PhC(=NCH2CN)H, prepared starting from aldehydes rather than ketones, yield the expected phenylacetonitrile even at temperatures as low as 120°C. Evidence for the mechanism comes from a study of the reactivity of the postulated intermediates: 2-cyano-3-phenylaziridine 4c, and 2,2-diphenyl-2H-azirine 5b. The route involving aziridine 4c is ruled out, since this compound does not react at all under the investigated conditions. The 2H-azirine 5b instead, yields the corresponding diphenylacetonitrile in DMF with K2CO3, at 150°C. The transformation seems to involve an initial deprotonation, followed by an intramolecular ring closure-CN elimination step, which yields the 2H-azirine. The azirine then isomerizes to the nitrile. Additional evidence for the intermediacy of the 2H-azirine, based on 1H NMR monitoring of the reaction 1 → 2, is described. Finally, the results of a simple isotope exchange experiment provide a rationale for the previously observed scrambling of labels, and further confirm the proposed mechanism.
Preparation of N-H aziridines in high enantiomeric excess by in situ aziridine-azirine-aziridine interconversion
Atkinson, Robert S.,Coogan, Michael P.,Lochrie, Ian S. T.
, p. 789 - 790 (2007/10/03)
Aziridine 6 is produced highly diastereoselectively by treatment of enantiopure 3-acetoxyaminoquinazolinone 4 (Q*NHOAc) with β-trimethylsilylstyrene: desilylative elimination of Q* and in situ addition of cyanide to the intermediate azirine gives the NH-a
Reaction of Hydrogen Fluoride in Pyridine Solution with cis-Cyano-2- and cis-Amido-2-aziridines. Preparation of β-Fluoro-α-amino Acids and Esters by Means of Acidic Hydrolysis and Alcoholysis of β-Fluoro-α-Amino Nitriles and/or β-Fluoro-α-Amino Acid Amide
Ayi, Ayicoue I.,Guedj, Roger
, p. 2045 - 2051 (2007/10/02)
The addition of hydrogen fluoride generated from pyridinium poly(hydrogen fluoride) (i.e.Olah's reagent) to some cis-2-cyano- and cis-2-amido-aziridines has been examined.The reaction led to fluoroamine derivatives which upon acidic hydrolysis and alcohol
Reactivite des N-vinylaziridines fonctionalisees. Synthese de derives des α,β-dehydro α-amino acides
Gelas-Mialhe, Yvonne,Touraud, Evelyne,Vessiere, Roger
, p. 2830 - 2851 (2007/10/02)
Secondary 2-cyano- and 2-ethoxycarbonylaziridines react with acetylenic compounds and activated vinylic chlorides to gives 2-cyano and 2-ethoxycarbonyl N-vinylaziridines.The nucleophile-catalysed isomerization of these compounds generally gives α,β-dehydr
