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Paper | Special issue | Vol 103, No. 2, 2021, pp.952-964
Published online, 22nd February, 2021
DOI: 10.3987/COM-20-S(K)64
A Theoretical Study of Product Selectivity in Rhodium Catalyzed Oxidative Coupling Reaction Caused by the Solvation Effect

Masahiro Higashi,* Naoto Shibata, Suguru Takeno, Tetsuya Satoh, Masahiro Miura, and Hirofumi Sato*

*Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoudai-katsura, Nishikyo, Kyoto 615-8510, Japan

Abstract

Solvation effects in the direct oxidative coupling of 1-phenylpyrazole with alkynes in the presence of rhodium catalyst was theoretically studied by means of the reference interaction site model self-consistent field with spatial electron density distribution (RISM-SCF-SEDD) method, which provides both of quantum chemical and statistical mechanical information on the solvation system. This reaction gives naphthalene and quinoline derivatives whose yields depend on the solvent environment. The computational results showed that the path for the naphthalene derivative is exothermic independently of solvent environment. On the other hand, the reaction energy of the reductive elimination for the quinoline derivative is considerably affected by solvation and endothermic in N,N- dimethylformamide (DMF) solution, indicating that the reaction is not preferable in DMF solution. The detailed analysis of solvation free energy and solvation structure are also reported.