Synthesis, Spectroscopic Characterization, and Reactivity of Water-Tolerant Eu3+-Based Precatalysts
Synthesis, Spectroscopic Characterization, and Reactivity of Water-Tolerant Eu3+-Based Precatalysts
复制标题
DOI：
10.1021/ic500790q
复制
发表时间：
2014-06-16
影响因子：
4.6
通讯作者：
Allen, Matthew J.
中科院分区：
文献类型：
--
作者：
Averill, Derek J.;Allen, Matthew J.
我们报告了在一组新的手性配体存在下，Eu3+ 的合成、光谱表征和反应性，这些配体专为水性、对映选择性 Mukaiyama 醇醛反应而设计。使用发光和核磁共振测量来表征基于 Eu3+ 的预催化剂的配位环境，并将该数据与产率和立体选择性进行比较。除了结构-功能关系之外，我们发现，在过量六齿配体存在下，Eu3+ 配位饱和，随后预催化剂的反应活性降低。这些发现有助于设计结合 Eu3+ 而不使 Eu3+ 配位球饱和的新配体。
We report the synthesis, spectroscopic characterization, and reactivity of Eu3+ in the presence of a new set of chiral ligands designed for the aqueous, enantioselective Mukaiyama aldol reaction. Luminescence and NMR measurements were used to characterize the coordination environments of the Eu3+-based precatalysts, and this data is compared with yields and stereoselectivities. In addition to structure-function relationships, we found that, in the presence of excess hexadentate ligands, Eu3+ is coordinatively saturated, and subsequently, the reactivity of the precatalysts is reduced. These findings are helpful for the design of new ligands that bind Eu3+ without saturating the Eu3+ coordination sphere.