Observations on the geometry of hydrogen transfer in (1,5) sigmatropic rearrangements

Journal Article · Wed Aug 25 00:00:00 EDT 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00381a026· OSTI ID:6234310

Kwart, Dt ^[1]; Brechbiel, M W; Acheson, R M; Ward, D C

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1. Univ. of Delaware, Newark

The present investigation was undertaken with the objective of identifying a (1,5) sigmatropic rearrangement occurring in a cyclic system which is not capable of such distention of the ..pi.. framework. The case for study was the rearrangement of the 9aH-quinolizine to the 4H-quinolizine. The temperature dependence of the isotope effect was again applied as the criterion of TS/sup + +/ geometry in H transfer. It has frequently been demonstrated, though not directly derivable (at present) from conventional transition-state theory of the isotope effect, that a bent TS/sup + +/, i.e., one involving H transfer at an acute angle, can be correlated with a temperature-independent k/sub H//k/sub D/. That is to say, the finding of isotope effect parameters of (..delta..E/sub a/)/sup H//sub D/ approx. = 0 and A/sub H//A/sub D/>>1.2 has been empirically shown to be most congruent with a bent TS/sup + +/.

• OSTI ID: 6234310
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
AZINES
DEUTERIUM
GEOMETRY
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MATHEMATICS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
QUINOLINES
STABLE ISOTOPES
TEMPERATURE DEPENDENCE