Neues über den Mechanismus der retentiven Substitution am Dreiring von Propellanen. Vorläufige Mitteilung

✍ Scribed by Hans Jörg Lindner; Brigitte Kitschke; Michael Liesner; Dieter Seebach

• Publisher: John Wiley and Sons
• Year: 1977
• Tongue: German
• Weight: 208 KB
• Volume: 60
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19770600402

✦ Synopsis

New results concerning the mechanism of retentive substitution at the three membered ring of propellanes

The reaction of the endo‐ and exo‐bromide 1a and 1b with acetate ion in aprotic polar solvents carried out at high concentrations of 1 furnishes the dimeric dehydro‐halogenation products 3a and 3b, the structures of which are determined by x‐ray crystallography (Fig. 1). The formation of 3a and 3b as well as of the products 2 of a retentive substitution process can be explained by assuming that the strained benzo‐tropones 4 are intermediates. Their high barrier to inversion is confirmed by π‐SCF‐molecular mechanics calculations.