Base catalysed decomposition of oxaziridines to yield N-unsubstituted aldimines

A Journey from Thermally Tunable Synthesis to Spectroscopy of Phenylmethanimine in Gas Phase and Solution

“…[17][18][19][20][21] The NÀHi mine derivatives of aliphatic or aromatic aldehydes are known to be much less stable, ando nly in af ew cases they have been successfully isolatedo rc haracterized. [22,23] Indeed, the literature is richo fe xamples supporting the instability and reactivity of these imines. The chemical labile nature of NÀHi mines, and the difficulties relatedt ot heir isolation,r esulted in the employment of imines possessingv arious substituents on the nitrogen atom (N-substituted imines).…”

“…This is due to the high reactivity of the imine intermediate [17–21] . The N−H imine derivatives of aliphatic or aromatic aldehydes are known to be much less stable, and only in a few cases they have been successfully isolated or characterized [22, 23] . Indeed, the literature is rich of examples supporting the instability and reactivity of these imines.…”

Deamination of the Amino Acid Fragment in Imine Metallacycles: Unexpected Synthesis of an NH‐Aldimine Organometallic Compound

“…[13] Only two NH aldimines have been isolated, in both cases at low temperatures. [16,17] Recently, Brown and co-workers reported the synthesis of stable adducts of these imines with boranes, as new intermediates for organic synthesis, [18] and Milstein and co-workers described the synthesis of a coordination compound of PhCH=NH by nonsymmetrical rhodium-mediated NÀN bond cleavage of aromatic azines. [19] With few exceptions, amino acid biodegradation involves the removal of the a-amino group to give the corresponding a-keto acid, and imines act as intermediates in this process.…”

Characterization and Utility of N‐Unsubstituted Imines Synthesized from Alkyl Azides by Ruthenium Catalysis

“…This observation is in sharp contrast to the previous reports which described only cis-4 as a very unstable species. [3] Lowering the temperature somewhat increased the relative ratio of cis-4. On the basis of the relative integration of the peaks in the NMR spectrum of the crude reaction mixture, the DG value between two geometrical isomers in [D 8 ]THF was determined to be about 1 kcal mol À1 .…”

“…This feature is easily addressed by the fact that only few N-unsubstituted imines have been successfully isolated or characterized. [3,4] In fact, such imines have been proposed as an intermediate without isolation (or detection) in most cases. For example, Chen and Brown, [5] and Itsuno et al [6] suggested that N-unsubstituted imines could be formed from the N-trialkylsilyl imine precursors, but the scope of this method is restricted to the preparation of non-enolizable imines.…”