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Mechanistic investigations aided by isotopic labeling. 10. Investigations of novel furan-2,3-dione rearrangements by oxygen-17 labeling

Journal Article · · Journal of Organic Chemistry; (United States)
DOI:https://doi.org/10.1021/jo00001a044· OSTI ID:7237525
; ;  [1]
  1. Karl Franzens Univ., Graz (Austria)

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 {sup 17}O-labeling experiments using {sup 17}O NMR spectroscopic and mass spectroscopic measurements. Comparison of the {sup 17}O chemical shifts in (1), labeled either at the benzoyl and ring oxygens (1a-{sup 17}O) or at both exocyclic ring-carbonyl oxygens (1b-{sup 17}O), with those in the products (2-4) confirmed the proposed pathways of these rearrangements. Reactions involving carbodiimides, isocyanates, and ketene imines were investigated.

OSTI ID:
7237525
Journal Information:
Journal of Organic Chemistry; (United States), Journal Name: Journal of Organic Chemistry; (United States) Vol. 56:1; ISSN JOCEA; ISSN 0022-3263
Country of Publication:
United States
Language:
English