A Case of Competitive Aromatization vs. Sigmatropic [1,5]-Hydrogen Atom Migration in a 1,2,4-Cyclohexatriene Intermediate Derived from a Bis-Enyne Cyclization
1,2,4-Cyclohexatrienes are strained, reactive intermediates often formed by the tetradehydro-Diels–Alder (TDDA) reaction of a conjugated enyne bearing a tethered alkyne as the enynophile. The ene component is commonly the π-bond of an aromatic group. In this focused study, we investigated the reacti...
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| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-06-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/12/2610 |
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| Summary: | 1,2,4-Cyclohexatrienes are strained, reactive intermediates often formed by the tetradehydro-Diels–Alder (TDDA) reaction of a conjugated enyne bearing a tethered alkyne as the enynophile. The ene component is commonly the π-bond of an aromatic group. In this focused study, we investigated the reactivity of a symmetrical substrate in which the pair of terminal ene moieties were simple 2-propenyl groups. The intermediate 1,2,4-cyclohexatriene, now bearing a 5-isopropenyl group, underwent competitive aromatization (the most usual outcome of the strain-relieving event of the cyclohexatriene), along with an intramolecular [1,5]-hydrogen atom migration, ultimately producing a non-benzenoid, pyrrole derivative. This represents a previously unknown process for a 1,2,4-cyclohexatriene derivative. Mechanistic aspects of the competitive processes were revealed by experiments performed in the presence of various protic additives (MeOD and BHT). |
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| ISSN: | 1420-3049 |