A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety
文献类型：期刊论文
| 作者 | Remmerswaal, Wouter A.3,4; Nguyen, Thai-Tony3,4; Han, Zijian1; Slobodian, Fedor Krasovski3; Xiong, Ruisheng3; Kessler, Vadim2; Xu, Zhijian1; Zhu, Weiliang1; Erdelyi, Mate3,4 |
| 刊名 | CHEMPLUSCHEM
 |
| 出版日期 | 2025-08-04 |
| 页码 | 7 |
| 关键词 | density functional theory mechanism reactivity rearrangement |
| ISSN号 | 2192-6506 |
| DOI | 10.1002/cplu.202500252 |
| 英文摘要 | A previously unrecognized base-mediated rearrangement of a benzylic 1,5-hexadipyridynyl moiety is reported. Upon exposure to base, this structural motif rearranges into a constrained vinyl-pyridine substituted cyclobutene. Computational modeling indicates that the rearrangement takes place following a route involving stepwise deprotonation, shifted reprotonation, and 4 pi-electrocyclization. The reaction rate and the stereochemical outcome is consistent with the experimental observations. Furthermore, nonbase mediates rearrangements, through well-known Cope-like [3,3]-sigmatropic shifts, are found to be high in energy, and therefore, take a backseat to the base-mediated pathway. This rearrangement may provide a novel reactivity pathway of conjugated systems for synthetic methodology development. |
| WOS关键词 | THERMAL REARRANGEMENTS ; COPE REARRANGEMENT ; CHEMISTRY ; ACIDITIES ; ALLENES ; STATES |
| 资助项目 | Carl Trygger Foundation ; Swedish Research Council[2022-06725] ; Dutch Research Council[019.242EN.022] ; Disciplinary Domain of Medicine and Pharmacy ; Chinese Academy of Sciences ; NSFC-STINT joint project[82211530060] ; NSFC-STINT joint project[2025/5-155] ; [23:2764] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:001543086900001 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/321192]  |
| 专题 | 国家级研究中心_原创新药研究全国重点实验室 |
| 通讯作者 | Zhu, Weiliang; Erdelyi, Mate |
| 作者单位 | 1.Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, State Key Lab Drug Res, Shanghai 201203, Peoples R China 2.Bioctr Swedish Univ Agr Sci, Dept Mol Sci, S-75007 Uppsala, Sweden 3.Uppsala Univ, Dept Chem BMC, S-75123 Uppsala, Sweden 4.Uppsala Univ, Ctr Excellence Chem Mech Life, SE-75123 Uppsala, Sweden |
| 推荐引用方式 GB/T 7714 | Remmerswaal, Wouter A.,Nguyen, Thai-Tony,Han, Zijian,et al. A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety[J]. CHEMPLUSCHEM,2025:7. |
| APA | Remmerswaal, Wouter A..,Nguyen, Thai-Tony.,Han, Zijian.,Slobodian, Fedor Krasovski.,Xiong, Ruisheng.,...&Erdelyi, Mate.(2025).A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety.CHEMPLUSCHEM,7. |
| MLA | Remmerswaal, Wouter A.,et al."A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety".CHEMPLUSCHEM (2025):7. |
入库方式： OAI收割
来源：上海药物研究所
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