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

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Groenen, L.C. and Verboom, W. and Nijhuis, W.H.N. and Reinhoudt, D.N. and Hummel van, G.J. and Feil, D. (1988) The tertiary amino effect in heterocyclic synthesis : mechanistic and computational study of the formation of six-membered rings. Tetrahedron, 44 (14). pp. 4637-4644. ISSN 0040-4020

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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.
Item Type:Article
Copyright:© 1988 Elsevier Science
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Science and Technology (TNW)
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Link to this item:http://purl.utwente.nl/publications/70157
Official URL:http://dx.doi.org/10.1016/S0040-4020(01)86166-4
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