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AM1 studies on the intramolecular cyclization of ω‐haloenolate anions
Author(s) -
Lee Ikchoon,
Kim Chang Kon,
Kong Byung Hoo,
Lee Byung Choon
Publication year - 1991
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610040707
Subject(s) - chemistry , hsab theory , reactivity (psychology) , intramolecular force , medicinal chemistry , base (topology) , stereochemistry , crystallography , computational chemistry , medicine , mathematical analysis , alternative medicine , mathematics , pathology
The intramolecular cyclizations of ω‐haloenolate anions, − CαH 2 C(O)(CH 2 ) n−3 CωH 2 X with X = F, Cl and Br and n = 3–7, were investigated by the AM1 method. In most cases, cycloketone formation proceeds more favourably than cycloether formation, as predicted by the HSAB principle. The reactivity increases in the order X = F < Br < Cl for both processes, and for cycloether formation it is in the order n = 3 < 4 < 7 < 6 < 5 for all X but the relative order for n = 5 and 6 reverses in favour of n = 6 for cycloketone formation with X = Cl and Br. The softness of the acid centre, C ω , decreases for a harder X( = F) whereas it increases for a softer X( = Br). Thus the reactivity order with respect to X suggests that the softness of the base centres O and C α belongs to the borderline class. The transition state (TS) structures indicate that the BEP principle is obeyed in all cases, and a less reactive process has a more product‐like TS.