The tertiary amino effect in heterocyclic synthesis: mechanistic and computational study of the formation of six-membered rings

L.C. Groenen, Willem Verboom, W.H.N. Nijhuis, David Reinhoudt, G.J. van Hummel, D. Feil

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Abstract

The mechanism of the ring closure of [2-(1-pyrrolidinyl)phenylmethylene]-propanedinitrile (2a) to l,2,3,3a,4,5-hexahydropyrrolo[1,2-a]quinoline-4,4-dicarbonitrile (3a) has been studied by kinetic measurements using 1H-NMR spectroscopy. It could be shown that the rate-determining step consists of an intramolecular 1,5 hydrogen transfer, which is accompanied by charge separation within the- molecule. The calculated (AM1) and experimental (X-ray) molecular structure of 2a are in fairly good agreement. In the ground state geometry a 1,5 hydrogen transfer will most likely take place suprafacially. Subsequent rotation of the former vinyl group and C-C-bond formation, leading to a six-membered ring, also take place in a stereochemically defined way.
Original languageEnglish
Pages (from-to)4637-4644
JournalTetrahedron
Volume44
Issue number14
DOIs
Publication statusPublished - 1988

Keywords

  • IR-70157

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