Imidoylketene: An ab initio study of its conformations and reactions

Sihyun Ham, David M. Birney

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MP4(SDQ)/6-31G**//MP2/6-31G** calculations on the conformations of imidoylketene (1) as well as transition structures for several of its reactions are reported. Anti-Z-1 and anti-E-1 are of equal energy, while syn-Z-1 and syn-E-1 are respectively 2.0 and 0.5 kcal/mol higher. As the nitrogen analog of formylketene (2), the reactivity of 1 is modified from that of 2. While the nitrogen in 1 is more basic and nucleophilic than the oxygen in 2, greater resonance donation from the nitrogen decreases the electrophilicity of the ketene carbon in 1 relative to 2. Thus the barriers for the addition of water (6.3 kcal/mol) and of formaldehyde (10.6 kcal/mol) to 1 are very similar to those previously calculated for their respective additions to 2. Transition structures for the 1,3-hydrogen shifts of 3-amino-1,2-propadien-1-one (5a) and formylketene imine (6a) to give 1 were also located. The barriers to these reactions, (41.0 and 48.6 kcal/mol, respectively) are higher than those of the analogous reactions to form 2; reasons for these trends are discussed. The transition structures for these reactions are all planar or nearly so, reflecting the pseudopericyclic orbital topology which makes all the reactions allowed.

Original languageEnglish
Pages (from-to)3962-3968
Number of pages7
JournalJournal of Organic Chemistry
Issue number12
StatePublished - Jun 14 1996


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