| Autor: |
Jeong Kyun Im, Jun-Ho Choi, Won-jin Chung |
| Jazyk: |
angličtina |
| Rok vydání: |
2024 |
| Předmět: |
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| Zdroj: |
Communications Chemistry, Vol 7, Iss 1, Pp 1-7 (2024) |
| Druh dokumentu: |
article |
| ISSN: |
2399-3669 |
| DOI: |
10.1038/s42004-024-01365-2 |
| Popis: |
Abstract Alteration of a well-established reaction mechanism for access to different molecular structures is an inherently intriguing research subject. In that context, syn-stereospecific alkene dihalogenation draws attention as a long-standing problem in synthetic organic chemistry. The simplest approach would be the incorporation of an additional stereo-inverting step within the traditional anti-dihalogenation process. Surprisingly, this seemingly trivial idea turned out challenging, and no suitable stereo-directing group was known before our work. Herein, we describe a highly efficient syn-dichlorination of N-protected allylic amines through the anchimeric assistant phenomenon that has been inapplicable to alkene dihalogenation. Upon rational identification of a superior stereo-director, 1,8-naphthalimide, our practical reaction conditions with mild and convenient dichlorinating reagents can accommodate the formerly unemployable aryl alkenes in excellent yields (>95%) and stereospecificity (>50:1). DFT calculation suggests a concerted internal trapping mechanism without a discrete carbocationic species, which accounts for the conservation of the stereochemical integrity. |
| Databáze: |
Directory of Open Access Journals |
| Externí odkaz: |
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