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Theoretical studies on the intramolecular cyclization of alkyl halide anions

✍ Scribed by Ikchoon Lee; Chang Kon Kim

Publisher
John Wiley and Sons
Year
1990
Tongue
English
Weight
439 KB
Volume
11
Category
Article
ISSN
0192-8651

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✦ Synopsis

The intramolecular cyclization reactions of alkyl fluoride and chloride anions' were investigated theoretically using the AM1 method. Formation of five-membered ring was the most reactive and that of threemembered ring was the least reactive process in both series. For the fluoride series the reactivity order of n = 5 > 6 > 7 > 4 > 3 was dictated by the enthalpy (AHt) effect while for the chloride series the entropy (AS $) effect was found to play somewhat greater role due to the much better leaving ability of the chloride anion leading to the reactivity order of n = 5 > 6 7 4 > 7 > 3. For both series, BEP principle held and the degree of bond formation was greater with the fluoride series owing to the poor electron acceptor ability of the cleaving bond.

RESULTS AND DISCUSSION

All the intramolecular cyclization reactions studied were found to proceed through potential energy surface with loose reactant (RC) and product complexes (PC) and a TS in between; a represen-

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