Air Oxidation of N-Cyclopropylanilines

Selective Carbon–Carbon Bond Cleavage of Cyclopropylamine Derivatives

“…233 Indeed, N-cyclopropylanilines are readily prone to decomposition in air, as reported by Blackburn and co-workers (Scheme 73B). 234 In this work, simple aerobic oxidation of Ncyclopropylanilines 296 gave β-hydroxypropionamides 299 and dehomologated products 300. A plausible pathway involves base-mediated decomposition of cyclic peroxide 297 to form alkoxide 298.…”

Design, synthesis and evaluation of tryptophan analogues as tool compounds to study IDO1 activity

“…Other groups have noted the instability of aryl cyclopropyl amines under aerobic conditions – the position of the amine adjacent to the cyclopropane was identified as key for radical-based product degradation. 57 Determining the identity of the degradation product was beyond the scope of the investigation and the sample was taken forward and subjected to biochemical evaluation.…”

“…Other groups have noted the instability of aryl cyclopropyl amines under aerobic conditions -the position of the amine adjacent to the cyclopropane was identified as key for radicalbased product degradation. 57 Determining the identity of the Subsequent DIBAL-H mediated reduction of nitrile 36 followed by a Strecker reaction of the resulting aldehyde 37 afforded 17 in moderate yield as the hydrochloride salt (Scheme 5). 58,59 Inhibitor 17 was designed to overcome what was perceived to be the root of the instability of inhibitor 16: the presence of an amine directly attached to the cyclopropane.…”

Dirhodium(II)-catalyzed [3 + 2] cycloaddition of N-arylaminocyclopropane with alkyne derivatives

“…Meanwhile, since 1 contains a three-membered ring with high tension [3–6] and a nitrogen prone to single-electron oxidation, ring opening readily occurs followed by N -centered radical formation. The generated distonic radical cation can be further trapped by an alkene, alkyne, or triplet oxygen to initiate radical cyclization (Scheme 1) [7–15]. Thus, as key synthons, this class of molecules may play an important role in organic synthesis during construction of a series of aminocyclic compounds.…”