Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles
Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydri...
| Main Authors: | , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2023
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| Online Access: | https://hdl.handle.net/10356/164489 |
| _version_ | 1826129306364936192 |
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| author | Sekiguchi, Yoshiya Pang, Jia Hao Ng, Jia Sheng Chen, Jiahua Watanabe, Kohei Takita, Ryo Chiba, Shunsuke |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Sekiguchi, Yoshiya Pang, Jia Hao Ng, Jia Sheng Chen, Jiahua Watanabe, Kohei Takita, Ryo Chiba, Shunsuke |
| author_sort | Sekiguchi, Yoshiya |
| collection | NTU |
| description | Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center. |
| first_indexed | 2024-10-01T07:38:27Z |
| format | Journal Article |
| id | ntu-10356/164489 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:38:27Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | ntu-10356/1644892023-06-21T07:36:17Z Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles Sekiguchi, Yoshiya Pang, Jia Hao Ng, Jia Sheng Chen, Jiahua Watanabe, Kohei Takita, Ryo Chiba, Shunsuke School of Chemistry, Chemical Engineering and Biotechnology Engineering::Chemical engineering Dearomatization Beta-Hydride Elimination Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center. Ministry of Education (MOE) Nanyang Technological University Published version This work was supported by funding from Nanyang Technological University (NTU) (for S.C.) and the Singapore Ministry of Education (Academic Research Fund Tier 2: MOE2019-T2-1-089 for S.C.) as well as the Naito Foundation (for R.T.). 2023-01-30T02:24:16Z 2023-01-30T02:24:16Z 2022 Journal Article Sekiguchi, Y., Pang, J. H., Ng, J. S., Chen, J., Watanabe, K., Takita, R. & Chiba, S. (2022). Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles. JACS Au, 2(12), 2758-2764. https://dx.doi.org/10.1021/jacsau.2c00487 2691-3704 https://hdl.handle.net/10356/164489 10.1021/jacsau.2c00487 36590271 2-s2.0-85143488331 12 2 2758 2764 en MOE2019-T2-1-089 JACS Au © 2022 The Authors. Published by American Chemical Society. This is an open-access article distributed under the terms of the Creative Commons Attribution License. application/pdf |
| spellingShingle | Engineering::Chemical engineering Dearomatization Beta-Hydride Elimination Sekiguchi, Yoshiya Pang, Jia Hao Ng, Jia Sheng Chen, Jiahua Watanabe, Kohei Takita, Ryo Chiba, Shunsuke Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title | Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title_full | Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title_fullStr | Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title_full_unstemmed | Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title_short | Base-induced dehydrogenative and dearomative transformation of 1-naphthylmethylamines to 1,4-dihydronaphthalene-1-carbonitriles |
| title_sort | base induced dehydrogenative and dearomative transformation of 1 naphthylmethylamines to 1 4 dihydronaphthalene 1 carbonitriles |
| topic | Engineering::Chemical engineering Dearomatization Beta-Hydride Elimination |
| url | https://hdl.handle.net/10356/164489 |
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