Development of a new solvent effect estimation program capable of predicting reactivity and selectivity
| Project/Area Number |
17K05787
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Kochi University |
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Principal Investigator |
Kaneno Daisuke 高知大学, 教育研究部自然科学系理工学部門, 教授 (00361593)
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| Project Period (FY) |
2017-04-01 – 2023-03-31
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| Project Status |
Completed (Fiscal Year 2022)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
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| Keywords | 立体選択性 / 分子軌道計算 / 溶媒効果 / 量子化学計算 / 遷移状態 / ジアステレオ選択性 / 量子科学計算 / 有機化学 |
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| Outline of Final Research Achievements |
A new solvent effect calculation program was developed to parameterize the polarity and steric effects of solvents, and its validity was verified. The regioselective tricyanovinylation of pyrroles and the diastereoselective hydride reduction of ketones having a chiral center at the α-position were taken up as examples of reactions in which the difference in solvent species significantly affects the reaction selectivity, and were analyzed both experimentally and by molecular orbital calculations. In both reactions, a significant change in selectivity reversal and reaction rate was observed depending on the solvent species. The solvent effect calculation program developed in this study was applied to these reactions, and it was found that the steric effects of solvent molecules interacting with substrates and reagents are likely to affect the reactivity and selectivity of the reactions.
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| Academic Significance and Societal Importance of the Research Achievements |
本研究課題で作成した溶媒効果計算プログラムでは，溶媒分子の立体効果の重要性に着目し，極性効果と立体効果の２つのパラメータで高精度かつ高速に溶媒効果計算を行ことができる。特に溶媒の立体効果については，溶媒和のし易さ，溶媒の方向，溶媒和による反応阻害，の3つのパラメータという，これまでにない視点からの計算を行っている。有機化学反応の反応条件に用いる溶媒の最適化は多くの場合，経験に基づいたランダムスクリーニングによって行なわれているが，本プログラムを用いることにより，各種反応に適切な溶媒選択を理論的に行なうことが可能となり，反応予測や新規反応開発を行なう際の有力なツールになり得ると考えられる。
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Report
(7 results)
Research Products
(36 results)
