An evidence of the peroxidase-dependent oxygen transfer from hydrogen peroxide to sulfides

Examining Reactivity and Specificity of Cytochrome c Peroxidase by using Combinatorial Mutagenesis

“…[21, 32±35] Thioanisole is oxidized by peroxidases to the corresponding S-oxide and it has been shown that the ferryl oxygen atom of compound I of CCP and HRP is directly transferred to the thioether. [32,34,35] The reaction of the mutants with thioanisole was followed at pH 7 with 1 mM thioanisole and 1 mM H 2 O 2 . Thioanisole and the corresponding S-oxide were quantified by HPLC.…”

Single turnover studies of oxidative halophenol dehalogenation by horseradish peroxidase reveal a mechanism involving two consecutive one electron steps: Toward a functional halophenol bioremediation catalyst

“…(1)) [20]. A possible mechanism of this reaction could involve a direct oxygen transfer from HRP Cpd I to 2,4,6-TCP to generate 2,4-dichloro 1,4-benzoquinone in a single two-electron oxo transfer process [44,45]. An alternative mechanism involves two consecutive one-electron transfer steps with sequential formation of both HRP compounds I (HRP I) and II (HRP II), as initially proposed by Samokyszyn and co-workers [20].…”

Nuclear Magnetic Resonance Spectroscopic and Computational Investigations of Chloroperoxidase Catalyzed Regio- and Enantio-Selective Transformations

“…Chloroperoxidase (CPO), a heme protein secreted by the marine fungus Caldariomyces fumago [23], is one of the most versatile biocatalyst that catalyzes halogenation [23] in the presence of halide ion (except fluoride) and oxidation of a variety of substrates such as sulfides [41,197], alcohols [34], and arylamine [130]. This enzyme can be highly produced up to 1-1.5 g/liter using Blanke's method [111].…”

“…In particular, chloroperoxidase(CPO)-catalyzed oxidation of a prochiral sulfide is unquestionably a green and economical method for synthesizing enantiomerically pure sulfoxides [196], because CPO can use hydrogen peroxide as the oxidant without requiring a cofactor. In 1986, Kobayashi, et al first reported the enantioselective oxidation of methyl phenyl sulfides by CPO and hydrogen peroxide [197]. In 1992, a series of substituted sulfides suitable for enantioselective sulfoxidation was reported by Colonna et al [198].…”

“…Chloroperoxidase (CPO) itself catalyzes a broad class of reactions including halogenation [28], dehalogenation [39], N-demethylation [37], epoxidation of alkenes [42], dismutation of peroxide [31], and oxidation of organic compounds such as sulfides [197], alcohols [34], and amines [130]. A remarkable feature of CPO is to catalyze oxygen insertions with a high enantioselectivity in sulfoxidation [41,198] and epoxidation reactions [42,43], which offers a great potential in the synthesis of chiral compounds [46,109,133].…”