利用仿生N,N,O-配体进行铁催化的烯烃顺式二羟基化反应

Iron-catalyzed olefin cis-dihydroxylation using a bio-inspired N,N,O-ligand.

作者信息

Oldenburg Paul D, Shteinman Albert A, Que Lawrence

机构信息

Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.

出版信息

J Am Chem Soc. 2005 Nov 16;127(45):15672-3. doi: 10.1021/ja054947i.

DOI:10.1021/ja054947i

PMID:16277487

Abstract

Nature has evolved enzymes that carry out the cis-dihydroxylation of C=C bonds in the biodegradation of arenes in the environment. These enzymes, called Rieske dioxygenases, have mononuclear iron centers coordinated to a 2-His-1-carboxylate facial triad motif that has emerged as a common structural element among many nonheme iron enzymes. In contrast, olefin cis-dihydroxylation is conveniently carried out by OsO4 and related species in synthetic procedures. To develop more environmentally benign strategies for carrying out these transformations, we have designed Ph-DPAH [(di-(2-pyridyl)methyl)benzamide], a tridentate ligand that mimics the facial N,N,O site of the mononuclear iron center in the Rieske dioxygenases. Its iron(II) complex has been found to catalyze olefin cis-dihydroxylation almost exclusively and with high H2O2 conversion efficiency on a wide range of substrates. and 18O labeling experiments suggest the participation of an FeV oxidant.

摘要

自然界进化出了一些酶，它们在环境中芳烃的生物降解过程中催化碳 - 碳双键的顺式二羟基化反应。这些酶被称为 Rieske 双加氧酶，具有单核铁中心，该中心与一个 2 - 组氨酸 - 1 - 羧酸盐面三联体基序配位，这一基序已成为许多非血红素铁酶中的常见结构元件。相比之下，在合成过程中，烯烃的顺式二羟基化反应可方便地由四氧化锇及相关物质来实现。为了开发更环保的策略来进行这些转化，我们设计了 Ph - DPAH [（二 - （2 - 吡啶基）甲基）苯甲酰胺]，这是一种三齿配体，它模拟了 Rieske 双加氧酶中单核铁中心的面 N，N，O 位点。已发现其铁（II）配合物几乎能专一性地催化烯烃的顺式二羟基化反应，并且在多种底物上具有高的过氧化氢转化效率。18O 标记实验表明存在 FeV 氧化剂参与反应。