Heme compound II models in chemoselectivity and disproportionation reactions
Ranjana Gupta, Xiao‐Xi Li, Youngseob Lee, Mi Sook Seo, Yong‐Min Lee, Sachiko Yanagisawa, Minoru Kubo, Ritimukta Sarangi, Kyung‐Bin Cho, Shunichi Fukuzumi, Wonwoo Nam
Abstract
(OH)(TMP), and 2b becoming the active oxidant to conduct the cyclohexene epoxidation. In contrast to 2a, 1a does not disproportionate under the present reaction conditions. DFT calculations confirm that compound II models prefer C-H bond hydroxylation and that disproportionation of compound II models is controlled thermodynamically by the porphyrin ligands. Other aspects, such as acid and base effects on the disproportionation of compound II models, have been discussed as well.
Topics & Concepts
DisproportionationChemoselectivityPorphyrinLigand (biochemistry)ChemistryHemePhotochemistryStereochemistryOrganic chemistryCatalysisReceptorEnzymeBiochemistryMetal-Catalyzed Oxygenation MechanismsPorphyrin and Phthalocyanine ChemistryHemoglobin structure and function