Enantioselectivity in Ruthenium‐Catalyzed Propargylic Substitution Reactions of Propargylic Alcohols with Acetone: A DFT Study
- 21 September 2021
- journal article
- research article
- Published by Wiley in Chemistry – An Asian Journal
- Vol. 16 (22), 3760-3766
- https://doi.org/10.1002/asia.202100984
Abstract
The enantioselectivity in the propargylic substitution reactions of propargylic alcohols with acetone catalyzed by optically active thiolate-bridged diruthenium complexes was examined via ωB97X-D level DFT calculations. Some structures with intramolecular dispersion interactions between ligands were found for the ruthenium-allenylidene complex, which is the key intermediate in the catalytic reaction, and it was determined that the structure corresponding to the X-ray crystal structure, which had provided the transition state model for the enantioselectivity in previous studies, was not the most stable among the obtained structures. Then, a variety of transition-state structures for the nucleophilic attack of prop-1-ene-2-ol, which is the enol isomer of acetone, on the γ-carbon of the ruthenium-allenylidene complex were explored. Among the transition-state structures with lower energies, the number of structures leading to the major ( R ) product was found to be larger than that of structures leading to the minor ( S ) product, providing enantioselectivity in terms of probability distributions. The introduction of a phenyl group in the thiolate ligand was suggested to increase the selectivity. Thus, we propose the novel transition state model for the asymmetric catalytic reaction system.Keywords
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