2013 Fiscal Year Final Research Report
preparation of metal-oxo complex bearing tridentate ligand: development of asymmetric oxidation reaction assisted by additional ligand
| Project/Area Number |
24750096
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Synthetic chemistry
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| Research Institution | Institute of Physical and Chemical Research (2013)
Waseda University (2012) |
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Principal Investigator |
NIWA Takashi 独立行政法人理化学研究所, ライフサイエンス技術基盤研究センター, 研究員 (30584396)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Keywords | 不斉エポキシ化反応 / 不斉配位子 / 三座配位子 / ポルフィリン / 不斉酸化反応 |
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| Research Abstract |
On this study, an asymmetric oxidation catalyst controlled by an additional ligand was designed. Although iron-porphyrins are well-known catalysts for oxidations, application of them to asymmetric oxidation are difficult due to their planar structure.
I focused on CAZBOX ligand, which has porphyrin-like structure such as planarity and amide-ligands. After numerous attempts, I found that the iron-cazbox complexes catalyze asymmetric epoxidations of alkenes. Mechanistic analyses by ESR and UV present the cazbox ligands show similar reactivity to porphyrins on the oxidation reactions. Furthermore, studies on substituent effect of the ligand disclose that enantioselection of the product depend on electronic interaction between the cazbox ligand and the corresponding substrate. Through these studies, I have developed the chiral ligand CAZBOX bearing porphyrin-like reactivities.
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