2016 Fiscal Year Final Research Report
Development of novel fused planar-chiral catalysts and their asymmetric catalysis based on the concept of dynamism control
| Project/Area Number |
15K13649
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Organic chemistry
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| Research Institution | Waseda University |
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Principal Investigator |
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| Project Period (FY) |
2015-04-01 – 2017-03-31
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| Keywords | ピリジノファン / 面不斉 / 有機触媒 / 遠隔立体効果 / 不斉シクロプロパン化 / ラセミ化 / ピリジニウムイリド |
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| Outline of Final Research Achievements |
We have designed and synthesized novel planar-chiral parapyridinophane catalysts of the 2nd generation, whose ansa-bridges are tethered to a part of their pyridine rings to freeze their characteristic rope-skipping racemization even at higher temperatures. Pyridinophane catalysts fused with six membered ring effected highly enantioselective ylide-mediated cyclopropanation reactions to afford optically active trans-cyclopropanes exclusively with excellent enantiomeric excesses. For pyridinophane catalysts fused with five membered ring, their catalytic abilities were improved remarkably by introducing remote steric effect: incorporation of large substituents on such pyridine catalysts exerted a significant increase of enantioselectivity close to the level of the catalyst fused with six membered ring. Consequently, we have developed successfully novel fused pyridinophane catalysts with higher planar-chiral stability to achieve high level of asymmetric induction as organocatalysts.
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| Free Research Field |
有機化学
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