Stereospecific Synthesis of 2-Oxazinyl-4-oxoazetidinecarbamates Starting from a 1,2-Diazephine. A New Type of Intramolecular Transbenzoylation

Article abstract of DOI:10.1002/hlca.19880710418

Azetidinodiazepines 4b and 4c react with acylnitroso dienophiles 5a-c, specifically from their convexe α-side, but in a non-regiospecific way, leading thereby stereospecifically to the expected adducts 6a-d and 7a-d.The three-dimensional structures of 6a and 7a were determined by X-ray analyses which corroborated their NMR data.OsO4 cis-glycolization occured in good yield with the inverse adducts 7a and 7e and led to the rearranged products 10.These latter ones result from an intramolecular N- to O-transbenzoylation of the short-lived intermediates 9 followed by fragmentation of the aminal function.X-Ray analysis of 7a showed the N(10) atom to be pyramidal, a result which demonstrates that it does not have any pronounced benzamide character; otherwise no such N- to O-transbenzoylation would have taken place.Structure and relative configuration of 10a were ascertained by X-ray analysis which confirmed its NMR data as well as the stereochemical outcome of its formation.