Abstract
| - Single-electron transfer and hydrogen atom transfer pathways have been proposed to accountfor the cytochrome P450-catalyzed α-carbon oxidations of amines. With the aid of electrochemistry-electrospray ionization mass spectrometry, the electrochemical potentials required for the one-electronoxidations of N-methyl- and selected N-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridinyl derivatives and thechemical fates of the resulting aminyl radical cations have been investigated. Comparison of the results ofthese studies with those observed in the corresponding enzyme catalyzed oxidations suggests that aminylradical cations are not obligatory intermediates in the cytochrome P450-catalyzed α-carbon oxidations ofthis class of substrates.
|