Mechanistic Analysis of Oxidative C-H Cleavages Using Inter- and Intramolecular Kinetic Isotope Effects.

ABSTRACT: A series of monodeuterated benzylic and allylic ethers were subjected to oxidative carbon-hydrogen bond cleavage to determine the impact of structural variation on intramolecular kinetic isotope effects in DDQ-mediated cyclization reactions. These values are compared to the corresponding intermolecular kinetic isotope effects that were accessed through subjecting mixtures of non-deuterated and dideuterated substrates to the reaction conditions. The results indicate that carbon-hydrogen bond cleavage is rate determining and that a radical cation is most likely a key intermediate in the reaction mechanism.

SUBMITTER: Jung HH 

PROVIDER: S-EPMC2904620 | biostudies-literature | 2009 Dec

REPOSITORIES: biostudies-literature