Cycloadditions, 27. The Thermal Rearrangement of the Bicyclo[2.2.2]- to Bicyclo[3.2.1]octadiene Moiety in Tricyclic Lactams

✍ Scribed by Himbert, Gerhard ;Diehl, Klaus

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 634 KB
• Volume: 1997
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.199719970631

✦ Synopsis

Abstract

The tricyclic lactams 4a–h, possessing a bicyclo[2.2.2]octadiene moiety, obtained by intramolecular Diels‐Alder reaction of the vinylidene malondiamides 1a–h, generally isomerize in boiling xylene to give the new lactams 7a–h, now bearing a bicyclo[3.2.1]octadiene part. The difference in the rates of the isomerizations 4 → 7 and the results with the nitro ‐ and methoxy‐substituted derivatives 4i–l are in accordance with the proposed intermediate zwitterion 6, which is formed by the migration of one vinyl group from position 1 to position 5 of the lactam moiety.