2013 Fiscal Year Final Research Report
Microscopic Analysis of Dynamics-Controlled Organic Reactions
| Project/Area Number |
22350023
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Rikkyo University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
MOCHIZUKI Yuji 立教大学, 理学部, 教授 (00434209)
KOMEIJI Yuto 独立行政法人産業技術総合研究所, ナノシステム研究部門, 主任研究員 (30357032)
SATO Makoto 立教大学, 理学部, ポストドクトラルフェロー (10634347)
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| Project Period (FY) |
2010-04-01 – 2014-03-31
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| Keywords | 有機化学反応 / 量子化学 / シミュレーション / 遷移状態 / 溶媒効果 |
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| Research Abstract |
A combined computational-experimental study was carried out to examine dynamics effects in organic reactions. A fragment molecular orbital-molecular dynamics method (FMO-MD) was developed and used to analyze microscopic reaction mechanisms, in particular the active role of solvent molecules, in amination and hydration reactions of aldehyde in water. Ab initio MD simulations were performed for selected organic reactions, such as molecular rearrangement, elimination, addition, and substitution reactions. These computational studies revealed that the reaction products were determined through path bifurcation after the rate-determining transition state. Experimental studies using kinetic measurements and product analyses gave the results that supported the conclusion on the basis of the MD simulations. These results demonstrated that reaction dynamics play important role in determining the reaction mechanism and may require modification of the traditional transition state theory.
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