On the reactivity of bromoperoxidase I (<em>Ascophyllum nodosum</em>) in buffered organic media: Formation of carbon bromine bonds

Hartung, Jens; Dumont, Yvonne; Greb, Marco; Hach, Diana; Köhler, Franz; Schulz, Heiko; Časný, Marian; Rehder, Dieter; Vilter, Hans

doi:10.1351/PAC-CON-08-09-01

Pure Appl. Chem., 2009, Vol. 81, No. 7, pp. 1251-1264

http://dx.doi.org/10.1351/PAC-CON-08-09-01

Published online 2009-06-29

On the reactivity of bromoperoxidase I (Ascophyllum nodosum) in buffered organic media: Formation of carbon bromine bonds

Jens Hartung¹*, Yvonne Dumont¹, Marco Greb², Diana Hach¹, Franz Köhler², Heiko Schulz¹, Marian Časný³, Dieter Rehder³ and Hans Vilter⁴

¹ Fachbereich Chemie, Organische Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße, 67663 Kaiserslautern, Germany
² Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
³ Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
⁴ Zurmaiener Straße 16, D-54292 Trier, Germany

Abstract: Peroxidase (PO) activity of vanadate(V)-dependent bromoperoxidase (BPO) I (Ascophyllum nodosum) [V_BrPO(AnI)] was retained with a half-life time of ~60 days, if stored in H₂O₂-incubated, morpholin-4-ethane sulfonic acid (MES)-buffered aqueous alcoholic solutions. These conditions were applied for converting bromide and, e.g., methyl pyrrole-2-carboxylate into bromopyrroles with an almost quantitative peroxide yield. δ,ε-unsaturated alcohols furnished β-bromohydrins and products of bromocyclization, i.e., tetrahydrofurans and tetrahydropyrans (70–84 % mass balance), if treated with H₂O₂, KBr, and V_BrPO(AnI) in phosphate-buffered, CH₃CN-diluted media.