Photoinduced Deracemization with Weak Interaction by Chiral Ruthenium(II) Complex

去消旋化是获得光学活性化合物的有效方法，而光去消旋化（包括光敏剂对映选择性还原和氧化）的报道较少。因此，本研究设计了一种用于光去消旋的光敏剂。三-联吡啶型钌（II）配合物作为光敏剂，具有对映体选择性的能力。在联吡啶配体中通过酯键引入了氨酰基作为光学活性基团。这种手性联吡啶配体被用于新型钌（II）光敏剂。合成了两种新的钌（II）配合物：单（手性联吡啶）钌（II）配合物和双（手性联吡啶）钌（II）配合物，研究了这两种钌（II）配合物的光化学和电化学性质，结果表明这两种配合物具有光敏剂的作用。这些钌（II）配合物被用作光敏剂，用于手性钴（III）配合物的光还原。钴（III）络合物被对映选择性地还原，并且很明显，这些钌（II）络合物可以用作光去外消旋化的光敏剂。此外，还研究了手性钌（II）配合物与手性锇（II）配合物之间的能量转移对映体选择性，获得了弱相互作用下的对映体选择性的认识，这些钌（II）配合物可应用于金属配合物的光去外消旋化，以及有机化合物的光去外消旋化。

A deracemization is the very effective method to obtain optical active compounds, however, there are few reports of the photo deracemization, which consists of the enantioselective reduction and oxidation with a photo sensitizer. Therefore, a photo sensitizer for the photo deracemization was designed in this research. The tris-bipyridine type ruthenium(II) complex was employed for the photo sensitizer, which possesses the enantioselective ability. The camphamoyl group was introduced into bipyridine ligand through the ester bond as an optically active group. This chiral bipyridine ligand was used for the novel ruthenium(II) photo sensitizer. Two ruthenium(II) complexes, mono(chiral bipyridine) ruthenium(II) complex and bis(chiral bipyridine) ruthenium(II) complex were newly synthesized.The photochemical and electrochemical properties of these ruthenium (II) complexes were investigated, and it was shown that these complexes could act as a photo sensitizer. These ruthenium (II) complexes were used as a photo sensitizer for the photo reduction of the chiral cobalt (III) complex. The cobalt (III) complex was reduced enantioselectively, and it is clear that these ruthenium(II) complexes can be used as a photo sensitizer for the photo deracemization. In addition, the enantioselective the energy transfer from the chiral ruthenium (II) complex to chiral osmium(II) complex was investigated to obtain knowledge about an enantioselection with a weak interaction.These ruthenium(II) complexes would be applied for the photo deracemization of the metal complexes, and that of organic compounds.