Heme compound II models in chemoselectivity and disproportionation reactions.

ABSTRACT: Heme compound II models bearing electron-deficient and -rich porphyrins, [Fe^IV(O)(TPFPP)(Cl)]^- (1a) and [Fe^IV(O)(TMP)(Cl)]^- (2a), respectively, are synthesized, spectroscopically characterized, and investigated in chemoselectivity and disproportionation reactions using cyclohexene as a mechanistic probe. Interestingly, cyclohexene oxidation by 1a occurs at the allylic C-H bonds with a high kinetic isotope effect (KIE) of 41, yielding 2-cyclohexen-1-ol product; this chemoselectivity is the same as that of nonheme iron(iv)-oxo intermediates. In contrast, as observed in heme compound I models, 2a yields cyclohexene oxide product with a KIE of 1, demonstrating a preference for C[double bond, length as m-dash]C epoxidation. The latter result is interp

SUBMITTER: Gupta R 

PROVIDER: S-EPMC9116367 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature