Keto–Enol Tautomerization Triggers an Electrophilic Aldehyde Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex
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چکیده
منابع مشابه
Mononuclear nonheme ferric-peroxo complex in aldehyde deformylation.
A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well.
متن کاملAn isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion.
Reaction of a nonheme iron(III)-peroxo complex, [Fe(III)(14-TMC)(O2)](+), with NO(+), a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2˙(-)) + NO], affords an iron(IV)-oxo complex, [Fe(IV)(14-TMC)(O)](2+), and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [Fe(III)(14-TMC)(NO3)(F)](+).
متن کاملCatalyzes a Tautomerization Reaction
Background: Recent studies of melanin biosynthesis have uncovered an unusual enzymatic activity which converts the non-naturally occurring D-isomer of 2-carboxy-2, 3-dihydroindole5,6-quinone (dopachrome) into 5,6-dihydroxyindole-2-carboxylic acid (DHICA). The aim of the present investigation was to isolate and characterize the enzyme catalyzing this tautomerization reaction. Materials and Metho...
متن کاملA Mononuclear Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Metal Ions.
Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxyg...
متن کاملA mononuclear nonheme cobalt(iii)-hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.
A mononuclear nonheme cobalt(iii)-hydroperoxide complex bearing a tetramethylated cyclam ligand, [(12-TMC)Co(III)(OOH)](2+), was synthesized and characterized spectroscopically and computationally; the cobalt(iii)-hydroperoxide complex exhibited an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.
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ژورنال
عنوان ژورنال: Journal of the American Chemical Society
سال: 2017
ISSN: 0002-7863,1520-5126
DOI: 10.1021/jacs.7b10033