Mechanistic insight into halide oxidation by non-heme iron complexes. Haloperoxidase versus halogenase activity.
نویسندگان
چکیده
This work presents the first detailed study on mechanistic aspects of halide oxidation by non-heme iron complexes. We show that while iron(III)-hydroperoxo complexes oxidise halides via oxygen atom transfer, the corresponding iron(IV)-oxo complex reacts via electron transfer.
منابع مشابه
Stringency of the 2-His–1-Asp Active-Site Motif in Prolyl 4-Hydroxylase
The non-heme iron(II) dioxygenase family of enzymes contain a common 2-His-1-carboxylate iron-binding motif. These enzymes catalyze a wide variety of oxidative reactions, such as the hydroxylation of aliphatic C-H bonds. Prolyl 4-hydroxylase (P4H) is an alpha-ketoglutarate-dependent iron(II) dioxygenase that catalyzes the post-translational hydroxylation of proline residues in protocollagen str...
متن کاملMechanistic Insight into Alcohol Oxidation by High-Valent Iron-Oxo Complexes of Heme and Nonheme LigandsThis research was supported by the Ministry of Science and Technology of Korea through Creative Research Initiative Program.
High-valent iron–oxo species are frequently invoked as the key intermediates in the catalytic oxidation of organic substrates by heme and nonheme iron mono-oxygenases. In the case of heme-containing enzymes such as cytochromes P450, oxoiron(iv) porphyrin p-cation radicals have been proposed as active oxidants that effect a number of oxidation reactions, which include alkane hydroxylation, olefi...
متن کاملFunctional Models for Vanadium Haloperoxidase: Reactivity and Mechanism of Halide Oxidation
A series of oxoperoxovanadium(V) complexes (ligands: H3nta ) nitrilotriacetic acid, H3heida ) N-(2hydroxyethyl)iminodiacetic acid, H2ada ) N-(2-amidomethyl)iminodiacetic acid, Hbpg ) N,N-bis(2-pyridylmethyl)glycine, and tpa ) N,N,N-tris(2-pyridylmethyl)amine) were characterized as functional models for the vanadium haloperoxidase enzymes. The crystal structures of K[VO(O2)Hheida], K[VO(O2)ada],...
متن کاملStructural Perspective on Enzymatic Halogenation
Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% ( Harris , C. M. ; Kannan , R. ; Kopecka , H. ; Harris , T. M. J. Am. ...
متن کاملDirect nitration and azidation of aliphatic carbons by an iron-dependent halogenase
Iron-dependent halogenases employ cis-halo-Fe(IV)-oxo (haloferryl) complexes to functionalize unactivated aliphatic carbon centers, a capability elusive to synthetic chemists. Halogenation requires (i) coordination of a halide anion (Cl(-) or Br(-)) to the enzyme's Fe(II) cofactor, (ii) coupled activation of O2 and decarboxylation of α-ketoglutarate to generate the haloferryl intermediate, (iii...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 49 93 شماره
صفحات -
تاریخ انتشار 2013