Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion
Since the groundbreaking discovery in 2018 that the synthesis of a bottleable nucleophilic aluminyl anion is feasible, a handful of derivatives have been developed to date, which are, however, limited to diamino- and dialkyl-substituted species. Herein, we report the synthesis of a cyclic (alkyl)(am...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2021
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| Online Access: | https://hdl.handle.net/10356/151894 |
| _version_ | 1811685477165563904 |
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| author | Koshino, Kota Kinjo, Rei |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Koshino, Kota Kinjo, Rei |
| author_sort | Koshino, Kota |
| collection | NTU |
| description | Since the groundbreaking discovery in 2018 that the synthesis of a bottleable nucleophilic aluminyl anion is feasible, a handful of derivatives have been developed to date, which are, however, limited to diamino- and dialkyl-substituted species. Herein, we report the synthesis of a cyclic (alkyl)(amino)aluminyl anion based on a five-membered framework. The dicoordinate aluminum center features both a lone pair of electrons and an unoccupied 3p orbital, thus genuinely making it isoelectronic with carbenes. We show the bond formation and bond activation at the Al sphere: thus, not only does it undergo electron redistribution with borane to furnish a heteroatomic group 13 ring exhibiting a σ-aromatic nature concomitant with a three-center two-electron AlB₂ bond but also the ambiphilic nature allows for oxidative addition of Si-H, N-H, and even C-C bonds at the aluminum center. |
| first_indexed | 2024-10-01T04:45:08Z |
| format | Journal Article |
| id | ntu-10356/151894 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T04:45:08Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | ntu-10356/1518942023-02-28T20:10:41Z Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion Koshino, Kota Kinjo, Rei School of Physical and Mathematical Sciences Science::Chemistry Anions Reaction Products Since the groundbreaking discovery in 2018 that the synthesis of a bottleable nucleophilic aluminyl anion is feasible, a handful of derivatives have been developed to date, which are, however, limited to diamino- and dialkyl-substituted species. Herein, we report the synthesis of a cyclic (alkyl)(amino)aluminyl anion based on a five-membered framework. The dicoordinate aluminum center features both a lone pair of electrons and an unoccupied 3p orbital, thus genuinely making it isoelectronic with carbenes. We show the bond formation and bond activation at the Al sphere: thus, not only does it undergo electron redistribution with borane to furnish a heteroatomic group 13 ring exhibiting a σ-aromatic nature concomitant with a three-center two-electron AlB₂ bond but also the ambiphilic nature allows for oxidative addition of Si-H, N-H, and even C-C bonds at the aluminum center. Ministry of Education (MOE) Nanyang Technological University Submitted/Accepted version We are grateful to Nanyang Technological University (NTU) and the Singapore Ministry of Education (MOE2018-T2-2-048(S)) for financial support. 2021-07-26T02:41:22Z 2021-07-26T02:41:22Z 2020 Journal Article Koshino, K. & Kinjo, R. (2020). Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion. Journal of the American Chemical Society, 142(19), 9057-9062. https://dx.doi.org/10.1021/jacs.0c03179 0002-7863 https://hdl.handle.net/10356/151894 10.1021/jacs.0c03179 32321239 2-s2.0-85086815126 19 142 9057 9062 en MOE2018-T2-2-048(S) Journal of the American Chemical Society This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.0c03179 application/pdf |
| spellingShingle | Science::Chemistry Anions Reaction Products Koshino, Kota Kinjo, Rei Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title | Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title_full | Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title_fullStr | Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title_full_unstemmed | Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title_short | Construction of σ-aromatic AlB₂ ring via borane coupling with a dicoordinate cyclic (alkyl)(amino)aluminyl anion |
| title_sort | construction of σ aromatic alb₂ ring via borane coupling with a dicoordinate cyclic alkyl amino aluminyl anion |
| topic | Science::Chemistry Anions Reaction Products |
| url | https://hdl.handle.net/10356/151894 |
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