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Fragmentation of Homoallylic Alkoxides. Thermolysis of potassium 2-substituted bicyclo [2.2.2]oct-5-en-2-alkoxides

✍ Scribed by Roger L. Snowden; Karl H. Schulte-Elte

Book ID
102856621
Publisher
John Wiley and Sons
Year
1981
Tongue
German
Weight
630 KB
Volume
64
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Thermolysis of the potassium 2‐substituted bicyclo [2.2.2]oct‐5‐en‐2‐alkoxides derived from alcohols 2–17 at 90–120° in hexamethylphosphoric triamide affords unsaturated ketones resulting from allylic bond cleavage. The mechanistic and synthetic aspects of this anionic fragmentation are discussed with reference to the formation of 1‐(3′‐cyclohexenyl)‐2‐alkanones 18–28 via initial heterolytic C(1), C(2)‐bond cleavage in the substrate alkoxide and regioselective, intramolecular protonation of the resultant transient allylic anion.

📜 SIMILAR VOLUMES

Fragmentation of Homoallylic Alkoxides.
Fragmentation of Homoallylic Alkoxides. Preparation of 1-(3′-cyclopentenyl)-2-alkanones from 2-substituted bicyclo[2.2.1]hept-5-en-2-ols
✍ Roger L. Snowden 📂 Article 📅 1983 🏛 John Wiley and Sons 🌐 German ⚖ 456 KB

## Abstract The potassium 2‐substituted bicyclo[2.2.1]hept‐5‐en‐2‐alkoxides derived from alcohols **2–9** at 30° in hexamethylphosphoric triamide (HMPA) afford 1‐(3′‐cyclopentenyl)‐2‐alkanones **10–19** __via__ heterolytic C(1), C(2)‐allylic bond cleavage in the substrate alkoxide followed by intra