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Nucleophilic Addition to C, C Double Bonds. Proximity and homoconjugative effects. Preliminary communication

✍ Scribed by Rolland A. Pfund; Camille Ganter

Publisher
John Wiley and Sons
Year
1979
Tongue
German
Weight
266 KB
Volume
62
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Proximity effects alone as well as in combination with electronic effects are responsible for the observed phenomenon of base‐catalyzed ether formation initiated by nucleophilic attack on a C, C double bond of the tricyclic olefin alcohols 1–10 (Scheme 1, Table 1).

With compounds 1–4, bearing a keto group, formation of the ethers 11–14 proceeds through a corresponding homoenolate b (Scheme 2) as an intermediate. In one case such a species could be trapped as the methyl ether 21 (Scheme 3).

Special attention is given to the stereochemical course of the homoketonization. Ring opening in 21 under acidic conditions occurs regioselectively, however non‐stereoselectively (Scheme 3). Full regio‐ and stereoselectivity (retention) is observed under basic conditions starting from the unsaturated keto alcohols 1 and 2 (Scheme 4) as well as from the keto ethers 11 and 12 (Scheme 5, Table 2).

📜 SIMILAR VOLUMES

nucleophilic addition to C,C-double bond
nucleophilic addition to C,C-double bonds. VII. Study of proximity effects in olefinic alcohols and amines by photoelectron spectroscopy
✍ Gerardo M. Ramos Tombo; Hans Jakob Ammann; Klaus Müller; Camille Ganter 📂 Article 📅 1983 🏛 John Wiley and Sons 🌐 German ⚖ 416 KB 👁 1 views

The influence of steric compression on electronic structure in polycyclic olefinic alcohols and amines is studied by PE. spectroscopy. The unsubstituted alcohol **2** and amine **7** show PE.‐spectroscopic properties that can be reconciled by postulating a predominance of intramolecularly H‐bonded

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✍ Gerardo M. Ramos Tombo; Camille Ganter 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 412 KB 👁 1 views

## Abstract The tricyclic olefinic primary amine **1** readily cyclizes to the tetracyclic secondary amine **2** at approximately 200° in protic as well as aprotic solvents although the C, C‐double bond is not activated by electron‐attracting groups. This unusual intramolecular addition is the cons