2023 Fiscal Year Annual Research Report
Rationally designed catalysis for the enantioselective activation of alkenes
| Project/Area Number |
21H01925
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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)
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| Project Period (FY) |
2021-04-01 – 2024-03-31
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| Keywords | Organocatalysis / Machine learning / Theoretical chemistry / Automated synthesis |
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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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