Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity
Endohedral metallofullerenes have excellent redox properties, which can be used to vary their reactivity to certain classes of molecules, such as alkyl halides. In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2023-12-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.19.138 |
| _version_ | 1827357245103407104 |
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| author | Yutaka Maeda Saeka Akita Mitsuaki Suzuki Michio Yamada Takeshi Akasaka Kaoru Kobayashi Shigeru Nagase |
| author_facet | Yutaka Maeda Saeka Akita Mitsuaki Suzuki Michio Yamada Takeshi Akasaka Kaoru Kobayashi Shigeru Nagase |
| author_sort | Yutaka Maeda |
| collection | DOAJ |
| description | Endohedral metallofullerenes have excellent redox properties, which can be used to vary their reactivity to certain classes of molecules, such as alkyl halides. In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5 with high regioselectivity. The products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction analysis of the single-bonded adduct 3a revealed the addition site of the p-methoxybenzyl group on La@C2v-C82. Theoretical calculations indicated that the addition site carbons in neutral La@C2v-C82 have high spin density, whereas those in the La@C2v-C82 anion do not have high charge densities. Thus, the reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1. |
| first_indexed | 2024-03-08T05:28:49Z |
| format | Article |
| id | doaj.art-4721dd7a4ac94d448c59821f426d323a |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-03-08T05:28:49Z |
| publishDate | 2023-12-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-4721dd7a4ac94d448c59821f426d323a2024-02-06T09:08:29ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972023-12-011911858186610.3762/bjoc.19.1381860-5397-19-138Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivityYutaka Maeda0Saeka Akita1Mitsuaki Suzuki2Michio Yamada3Takeshi Akasaka4Kaoru Kobayashi5Shigeru Nagase6Department of Chemistry, Tokyo Gakugei University, Koganei, Tokyo 184-8501, Japan Department of Chemistry, Tokyo Gakugei University, Koganei, Tokyo 184-8501, Japan Department of Chemistry, Josai University, Sakado, Saitama 350-0295, Japan Department of Chemistry, Tokyo Gakugei University, Koganei, Tokyo 184-8501, Japan Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577, Japan Department of Theoretical Studies, Institute for Molecular Science, Okazaki 444-8585, Japan Department of Theoretical Studies, Institute for Molecular Science, Okazaki 444-8585, Japan Endohedral metallofullerenes have excellent redox properties, which can be used to vary their reactivity to certain classes of molecules, such as alkyl halides. In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5 with high regioselectivity. The products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction analysis of the single-bonded adduct 3a revealed the addition site of the p-methoxybenzyl group on La@C2v-C82. Theoretical calculations indicated that the addition site carbons in neutral La@C2v-C82 have high spin density, whereas those in the La@C2v-C82 anion do not have high charge densities. Thus, the reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1.https://doi.org/10.3762/bjoc.19.138electron transfermetallofullereneradicalreduction |
| spellingShingle | Yutaka Maeda Saeka Akita Mitsuaki Suzuki Michio Yamada Takeshi Akasaka Kaoru Kobayashi Shigeru Nagase Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity Beilstein Journal of Organic Chemistry electron transfer metallofullerene radical reduction |
| title | Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity |
| title_full | Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity |
| title_fullStr | Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity |
| title_full_unstemmed | Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity |
| title_short | Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity |
| title_sort | controlling the reactivity of la c82 by reduction reaction of the la c82 anion with alkyl halide with high regioselectivity |
| topic | electron transfer metallofullerene radical reduction |
| url | https://doi.org/10.3762/bjoc.19.138 |
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