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一种生物质衍生的非贵金属钴催化剂,用于选择性还原烷基和(杂)芳基卤化物。

A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides.

机构信息

Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.

Process Chemistry and Catalysis, F. Hoffmann-La Roche Ltd., Grenzacherstrasse 124, 4070, Basel, Switzerland.

出版信息

Angew Chem Int Ed Engl. 2017 Sep 4;56(37):11242-11247. doi: 10.1002/anie.201702478. Epub 2017 Jun 30.

DOI:10.1002/anie.201702478
PMID:28517035
Abstract

Hydrodehalogenation is a straightforward approach for detoxifications of harmful anthropogenic organohalide-based pollutants, as well as removal of halide protecting groups used in multistep syntheses. A novel sustainable catalytic material was prepared from biowaste (chitosan) in combination with an earth-abundant cobalt salt. The heterogeneous catalyst was fully characterized by transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy measurements, and successfully applied to hydrodehalogenation of alkyl and (hetero)aryl halides with broad scope (>40 examples) and excellent chemoselectivity using molecular hydrogen as a reductant. The general usefulness of this method is demonstrated by successful detoxification of non-degradable pesticides and fire retardants. Moreover, the potential of the catalyst as a deprotection tool is demonstrated in a multistep synthesis of (±)-peronatin B (alkaloid).

摘要

水氘解是一种将有害人为有机卤代污染物解毒以及去除多步合成中使用的卤化物保护基的简单方法。一种新型的可持续催化材料是由生物废料(壳聚糖)与丰富的钴盐结合制备的。通过透射电子显微镜、X 射线衍射和 X 射线光电子能谱测量对非均相催化剂进行了全面表征,并成功应用于使用分子氢作为还原剂的烷基和(杂)芳基卤化物的水氘解,具有广泛的范围(>40 个实例)和优异的化学选择性。该方法的通用性通过成功解毒不可降解的农药和阻燃剂得到了证明。此外,该催化剂作为脱保护工具的潜力在(±)-peronatin B(生物碱)的多步合成中得到了证明。

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