Nucleophilic addition to C, C-double bonds. VI. Intramolecular addition of primary amines to C, C-double bonds induced by steric compression

✍ Scribed by Gerardo M. Ramos Tombo; Camille Ganter

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: German
• Weight: 412 KB
• Volume: 65
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19820650738

✦ Synopsis

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 consequence of the close proximity of the nucleophile and the double bond.

For the synthesis of the sterically highly hindered amine 1, the tricyclic oxime 4 was reduced with TiCl~3~ to the remarkably stable imine 5 and the latter treated with AlH~3~. On the other hand, reaction of 4 with AlH~3~ yielded the pentacyclic aziridine 6.