Rationally designed catalysis for the enantioselective activation of alkenes
| Project/Area Number |
21H01925
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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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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | Hokkaido University |
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Principal Investigator |
LIST BENJAMIN 北海道大学, 化学反応創成研究拠点, 特任教授 (80899253)
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| Co-Investigator(Kenkyū-buntansha) |
SIDOROV PAVEL 北海道大学, 化学反応創成研究拠点, 准教授 (30867619)
辻 信弥 北海道大学, 化学反応創成研究拠点, 特任准教授 (30873575)
長田 裕也 北海道大学, 化学反応創成研究拠点, 特任准教授 (60512762)
GIMADIEV TIMUR 北海道大学, 化学反応創成研究拠点, 博士研究員 (30874838)
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| Project Period (FY) |
2021-04-01 – 2024-03-31
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| Project Status |
Completed (Fiscal Year 2023)
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| Budget Amount *help |
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2023: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2022: ¥7,150,000 (Direct Cost: ¥5,500,000、Indirect Cost: ¥1,650,000)
Fiscal Year 2021: ¥8,060,000 (Direct Cost: ¥6,200,000、Indirect Cost: ¥1,860,000)
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| Keywords | Organocatalysis / Machine learning / Theoretical chemistry / Automated synthesis / Theoretical Chemistry / Synthetic Robot / Chemoinformatics |
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| Outline of Research at the Start |
The applicants will investigate catalytic enantiocontrol of carbocations generated by the activation of alkenes. In order to achieve this goal, catalysts having higher acidities and modifiable microenvironments will be designed and synthesized. A synthetic robot, theoretical calculations, machine learning would also be employed to accelerate the screening process, leading to a more efficient and rational design of asymmetric catalysis.
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| Outline of Annual Research Achievements |
Since we had already developed a platform to optimize catalyst structure based on existing training data, in the last fiscal year, we delved into the realm of quantum chemistry to further our understanding of catalyst optimization. Our particular focus was on quantitatively analyzing the pocket sizes of IDPi catalysts.
Traditionally, heteroatoms or aromatic substructures in substrates and reagents have been necessary to facilitate effective interactions with chiral catalysts. While confined acids have recently emerged as powerful tools for homogeneous asymmetric catalysis, catalyzing asymmetric reactions with purely aliphatic hydrocarbons, both as substrates and products, has remained unachieved. We developed an IDPi-catalyzed asymmetric cationic shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity.
During our investigation into such catalytic asymmetric cationic shifts of aliphatic hydrocarbons, we identified a potential correlation between the pocket size of the anion and stereoselectivities, albeit without quantitatively measuring each catalyst's pocket size. Building upon this observation, we employed the SambVca program to ascertain the Percent Buried Volume (%Vbur) of each anion, using a simplified substrate as a cation. As a result, we successfully validated the correlation between these two parameters.
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| Research Progress Status |
令和5年度が最終年度であるため、記入しない。
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| Strategy for Future Research Activity |
令和5年度が最終年度であるため、記入しない。
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Report
(3 results)
Research Products
(11 results)
