摘要:
The oxa 1,3-diene moiety in 4-benzoyl-5-phenylfuran-2,3-dione (1) adds aryl isocyanides or heterocumulenes via formal [4 + 1] or [4 + 2] cycloaddition processes. The unstable primary adducts undergo novel furandione rearrangements to intermediates in which the two oxygen atoms of the lactone moiety in 1 are equivalent. This equivalence was confirmed by O-17-labeling experiments using O-17 NMR spectroscopic and mass spectroscopic measurements. Comparison of the O-17 chemical shifts in 1, labeled either at the benzoyl and ring oxygens (1a-O-17) or at both exocyclic ring-carbonyl oxygens (1b-O-17), with those in the products 2-4 confirmed the proposed pathways of these rearrangements. Reactions involving carbodiimides, isocyanates, and ketene imines were investigated.