Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides

Article abstract of DOI:10.1021/jo00113a012

The scope of a recently discovered (Yoon, E.C. et al.J.Am.Chem.Soc. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs.Photolysis of N-<(trimethylsilyl)methyl>maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cycloaddition with 4.Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles.In contrast, photolysis of the nonconjugated cyclic imide, N-<(trimethylsilyl)methyl>succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30.On the other band, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35.Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34.In contrast, the nonconjugated imide, N-<(trimethylsilyl)methyl>-N-acetylacetamide (9), is unreactive upon irradiation.Similarly, simple N-<(trimethylsilyl)methyl>amides 10-13, while being photochemically labile, do not react to form "trappable" ylide intermediates upon irradiation.The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.