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Dimethyldioxirane reactions: Rate acceleration due to intramolecular H‐bonding
Author(s) -
Murray Robert W.,
Gu Hong
Publication year - 1996
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/(sici)1099-1395(199611)9:11<751::aid-poc844>3.0.co;2-a
Subject(s) - dimethyldioxirane , chemistry , intramolecular force , reaction rate constant , single bond , double bond , bond length , photochemistry , crystallography , computational chemistry , stereochemistry , medicinal chemistry , group (periodic table) , polymer chemistry , organic chemistry , kinetics , crystal structure , physics , quantum mechanics
Absolute rate studies were carried out on a series of C(SINGLE BOND)H insertion reactions of dimethyldioxirane (1a). The substrates were chosen so that the distance between a single tertiary C(SINGLE BOND)H bond and an OH group could be varied. The measured rate constants indicate that a rate acceleration occurs when the distance between the reacting C(SINGLE BOND)H bond and the OH group permits intramolecular H‐bonding stabilization of the transition state. A similar study in related compounds without the OH group showed no effect of chain length on the rate of the C(SINGLE BOND)H insertion reaction. A related study of the epoxidation reaction of la also found an increased rate when chain length permitted intramolecular H‐bonding by an OH group.