Premium
Kinetic and Stereochemistry of the SO 4 ⊙⊖ ‐Induced Hydroxylation of Cyclohexenes in Aqueous Solution
Author(s) -
Koltzenburg Günther,
Bastian Eugenie,
Steenken Steen
Publication year - 1988
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198810661
Subject(s) - hydroxylation , chemistry , aqueous solution , selectivity , hydrolysis , solvent , diffusion , ion , kinetic energy , stereochemistry , medicinal chemistry , organic chemistry , catalysis , enzyme , quantum mechanics , thermodynamics , physics
A largely solvent‐separated ion pair 3 is the presumed intermediate in the hydroxylation of cyclohexenes with SO 4 ⊙⊖ . Radical anions like 1 and 2 are formed in a nearly diffusion‐controlled step. They are subsequently hydrolyzed via 3. The axial/equatorial selectivity of the reaction of H 2 O with 3 is much greater than that observed in the reaction of OH ⊙ with 4‐ tert ‐butylcyclohexene (90:10 vs. 58:42).