Mechanism of RuO4-mediated oxidations of saturated hydrocarbons, isotope effects, solvent effects and substituent effects

✍ Scribed by Jan M. Bakke; Astrid E. Frøhaug

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 483 KB
• Volume: 9
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199607)9:7<507::aid-poc811>3.0.co;2-l

✦ Synopsis

Adamantane and 1,3,5,7-tetradeuterioadamantane were oxidized by RuO, in two solvent systems, CCI,-CH,CN-H,O and acetone-water, yielding two kinetic deuterium isotope effects (KIEs), 4.8 f 0.2 and 7.8 i 0-1, respectively, very similar to those obtained in analogous reactions with cis-decalin and perdeuteriocis-decalin, 4-8 and 6.8. These results were interpreted as primary KlEs and small or negligible secondary KIEs. From this, sp2-hybridized intermediates were not involved in the reaction path. The kinetic effect of the solvent was investigated by performing the reaction in aqueous acetone and acetonitrile. The rates were correlated with Grunwald-Winstein Y values and with Reichardt E,(30) values. Both correlations showed the reaction to be only moderately dependent on the solvent polarity. 1-Substituted adamantanes were oxidized in CCI,-CH3CN giving a Tart p* value of -2.5*0.1. These results were regarded as support for a reaction consisting of a pre-equilibrium with formation of a substrate-RuO, complex followed by a rate-determining concerted reaction.

The results did not support a reaction mechanism with a carbocation or radical intermediate, or a scheme with two competing reactions, one with a carbocation intermediate and the other with a concerted mechanism.