Stereoselective Assembly of Gigantic Chiral Molybdenum Blue Wheels Using Lanthanide ions and Amino Acids,Journal of the American Chemical Society

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Stereoselective Assembly of Gigantic Chiral Molybdenum Blue Wheels Using Lanthanide ions and Amino Acids
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-11-29 , DOI: 10.1021/jacs.8b09750
Weimin Xuan ₁ , Robert Pow ₁ , Nancy Watfa ₁ , Qi Zheng ₁ , Andrew J Surman ₁ , De-Liang Long ₁ , Leroy Cronin ₁

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The synthesis of chiral polyoxometalates (POMs) is a challenge because of the difficulty to induce the formation of intrinsically chiral metal-oxo frameworks. Herein we report the stereoselective synthesis of a series of gigantic chiral Mo Blue (MB) POM clusters 1–5 that are formed by exploiting the synergy between coordinating lanthanides ions as symmetry breakers to produce MBs with chiral frameworks decorated with amino acids ligands; these promote the selective formation of enantiopure MBs. All the compounds share the same framework archetype, based on {Mo124Ce4}, which forms an intrinsically chiral Δ or Λ configurations, controlled by the configurations of functionalized chiral amino acids. The chirality and stability of 1–5 in solution are confirmed by circular dichroism, 1H NMR, and electrospray ion mobility–mass spectrometry studies. In addition, the framework of the {Mo124Ce4} MB not only behaves as a host able to trap a chiral {Mo8} cluster that is not accessible by traditional synthesis but also promotes the transformation of tryptophan to kynurenine in situ. This work demonstrates the potential and applicability of our synthetic strategy to produce gigantic chiral POM clusters capable of host–guest chemistry and selective synthetic transformations.

中文翻译：

使用镧系离子和氨基酸立体选择性组装巨型手性钼蓝轮

手性多金属氧酸盐（POM）的合成是一个挑战，因为难以诱导本质手性金属氧骨架的形成。在此，我们报道了一系列巨大的手性钼蓝（MB）POM簇1-5的立体选择性合成，这些簇是通过利用配位镧系离子作为对称破坏者之间的协同作用来产生具有用氨基酸配体装饰的手性框架的MB；这些促进对映体纯MB的选择性形成。所有化合物共享相同的基于{Mo124Ce4}的框架原型，其形成本质上手性的Δ或Λ构型，由功能化手性氨基酸的构型控制。 1-5 在溶液中的手性和稳定性通过圆二色性、1H NMR 和电喷雾离子淌度-质谱研究得到证实。此外，{Mo124Ce4}MB的框架不仅充当能够捕获传统合成无法接近的手性{Mo8}簇的主体，而且还促进色氨酸原位转化为犬尿氨酸。这项工作证明了我们的合成策略的潜力和适用性，以产生能够进行主客体化学和选择性合成转化的巨大手性 POM 簇。

更新日期：2018-11-29

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