Absolute Asymmetric Synthesis: Protected Substrate Oxidation

Absolute Asymmetric Synthesis: Protected Substrate Oxidation
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DOI:
10.1002/chem.201406354
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发表时间:
2015-03-23
影响因子:
4.3
通讯作者:
Hakansson, Mikael
Hakansson, Mikael
中科院分区:
化学2区
文献类型:
--
作者:
Olsson, Susanne;Bjoremark, Per Martin;Hakansson, Mikael

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三个新的砾岩纳入双齿硫化物配体协调的Ru-II中心已被制备。通过缓慢结晶的完全自发拆分得到高度对映体富集的晶体批次,其用于硫化物配体的对映体选择性氧化,得到具有> 98%ee的手性亚砜络合物。所有相关的立体异构体已通过单晶X射线衍射、CD光谱和手性HPLC表征。如果配体的范围可以扩展到单齿硫化物,一个大规模的和可回收的方法,对映选择性氧化的硫化物可以设计。
Three new conglomerates incorporating bidentate sulfide ligands coordinated by Ru-II centers have been prepared. Total spontaneous resolution by slow crystallization gives highly enantioenriched crystal batches, which are used in enantioselective oxidation of the sulfide ligands to give chiral sulfoxide complexes with >98% ee. All relevant stereoisomers have been characterized by single-crystal X-ray diffraction, CD spectroscopy, and chiral HPLC. If the ligand range can be extended to monodentate sulfides, a large-scale and recyclable process for enantioselective oxidation of sulfides can be designed.