A Comparison between the Cycloadditions of Allenyl- and Vinyl-Cyclopentanes Using Density Functional Theory and GRRM Program.

Kazuki Watanabe, Yusuke Kawashima, Chisato Mukai, Tatsuya Takagi, Yukinori Suwa, Yu-Shi Tian, Norihito Kawashita

Chemical & pharmaceutical bulletin 2020

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Cycloaddition catalyzed by transition metals such as rhodium (I) is an important way to synthesize functionalized molecules in medicinal chemistry. When the reagent has a saturated ring containing more than five carbons (or heavy atoms), the reaction can progress when the compound has an allenyl group, but not for a vinyl group. Here, we constructed two computational models for allenylcyclopentane-alkyne and vinylcyclopentane-alkyne, and obtained their reaction pathways using density functional theory (DFT). From the reaction pathways, we confirmed that the former model has a much lower reaction energy than the latter. We also found that the molecular orbitals of the transition state structure at the rate-controlling step contribute significantly to the difference in reactivity between the two models.

Citation

Kazuki Watanabe, Yusuke Kawashima, Chisato Mukai, Tatsuya Takagi, Yukinori Suwa, Yu-Shi Tian, Norihito Kawashita. A Comparison between the Cycloadditions of Allenyl- and Vinyl-Cyclopentanes Using Density Functional Theory and GRRM Program. Chemical & pharmaceutical bulletin. 2020;68(8):737-741