One-Step Synthesis of Cyclobutene-Annulated Fullerenes through a Cascade Reaction |
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Authors: | Prof. Dr. Michio Yamada Yuta Uokawa Shino Sasaki Naohiro Iha Yoshihisa Hashimoto Yuya Nagasaki Prof. Dr. Yutaka Maeda Prof. Dr. Mitsuaki Suzuki |
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Affiliation: | 1. Department of Chemistry, Tokyo Gakugei University, Nukuikitamachi 4-1-1, Koganei, Tokyo, 184-8501 Japan;2. Department of Chemistry, Josai University, Sakado, Saitama, 350-0295 Japan |
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Abstract: | The physicochemical properties of fullerene-based materials typically vary depending on the type and mode of addition of functional groups; therefore, developing fullerene derivatives with novel structures is imperative for further progress in materials science. In this study, we develop an efficient one-step strategy for synthesizing cyclobutene-annulated fullerene derivatives (cyclobutenofullerenes) and characterize their electronic properties. Despite the steric strain, cyclobutenofullerenes can be easily prepared via a one-step reaction of C60 with a secondary propargylic phosphate. Structural analysis of the reaction intermediates suggests that the cascade reaction proceeds through a formal [2+2] cycloaddition of C60 with an allene, caused by the 1,3-migration of the propargylic phosphate, followed by an additional 1,3-migration and the subsequent 1,2-elimination of the phosphodiester moiety. |
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Keywords: | annulation π-conjugation cycloaddition Domino reaction rearrangement |
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