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Nucleophilic addition to C, C‐double bonds. VI . Intramolecular addition of primary amines to C, C‐double bonds induced by steric compression
Author(s) -
Tombo Gerardo M. Ramos,
Ganter Camille
Publication year - 1982
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19820650738
Subject(s) - chemistry , intramolecular force , steric effects , amine gas treating , double bond , aziridine , imine , nucleophile , oxime , nucleophilic addition , medicinal chemistry , stereochemistry , organic chemistry , ring (chemistry) , catalysis
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 .