| 研究実績の概要 |
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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