Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations
Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations
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DOI：
10.1021/acscatal.8b04667
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发表时间：
2019-04-01
期刊：
影响因子：
12.9
通讯作者：
Weck, Marcus
中科院分区：
文献类型：
--
作者：
Qu, Peiyuan;Kuepfert, Michael;Weck, Marcus
该贡献引入了基于聚（2-恶唑啉）的壳交联胶束（SCM）作为纳米反应器，以实现水介质中仲醇的一锅氧化还原驱动的去消旋化。 TEMPO 和 Rh-TsDPEN 部分在空间上分别位于亲水性冠和疏水性胶束核心中。 TEMPO 催化外消旋仲醇氧化成酮，而 Rh-TsDPEN 催化这些酮的不对称转移氢化 (ATH) 以提供对映体富集的仲醇。 Rh-TsDPEN 络合物和 TEMPO 这两种催化剂彼此不相容，SCM 旨在提供不可或缺的催化剂位点隔离。动力学研究表明，与相同反应条件下的无载体类似物相比，SCM 增强了固定化催化剂的反应活性。我们的纳米反应器可以对多种仲醇底物进行去消旋作用，并且可以连续重复使用，同时保持高活性。
This contribution introduces poly(2-oxazoline)-based shell cross-linked micelles (SCMs) as nanoreactors to realize one-pot redox-driven deracemizations of secondary alcohols in aqueous media. TEMPO and Rh-TsDPEN moieties are spatially positioned into the hydrophilic corona and the hydrophobic micelle core, respectively. TEMPO catalyzes the oxidation of racemic secondary alcohols into ketones, while Rh-TsDPEN catalyzes the asymmetric transfer hydrogenation (ATH) of these ketones to afford enantioenriched secondary alcohols. Both catalysts, the Rh-TsDPEN complex and TEMPO, are incompatible with each other and the SCMs are designed to provide indispensable catalyst site isolation. Kinetic studies show that the SCMs enhance the reactivity of the immobilized catalysts, in comparison to those for the unsupported analogues under the same reaction conditions. Our nanoreactors can perform deracemizations on a broad range of secondary alcohol substrates and are reusable in a continuous manner while maintaining high activity.