Die «Zip»-Reaktion: Eine neue Ringerweiterungsreaktion. Synthese von 17-, 21- und 25-gliedrigen Polyaminolactamen. 4. Mitteilung über Umamidierungsreaktionen

✍ Scribed by Urs Kramer†; Armin Guggisberg; Manfred Hesse; Hans Schmid†

• Publisher: John Wiley and Sons
• Year: 1978
• Tongue: German
• Weight: 687 KB
• Volume: 61
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19780610417

✦ Synopsis

The Zip‐reaction: A New Method for the Synthesis of Macrocyclic Polyaminolactams

The 21‐ and 25‐membered aminolactams 11 and 25 were synthesized from the 13‐membered lactam 4. To introduce the ring enlargement unit (a propylamino group) 4 was N‐alkylated using acrylonitrile and the resulting product hydrogenated. Repetition of this reaction sequence gave 3, which was converted in the presence of base in 90% yield to the ring‐enlarged macrocyclic base 11 (Scheme 2). In a similar but stepwise synthesis consisting of two separate ring‐enlargement reactions 4 was transformed to 11 via 13 (Scheme 4). Introducing three ringenlargement units into 4 the 25‐membered aminolactam 25 was synthesized in 84% yield (Scheme 5). The mechanism of the ring‐enlargement reaction is given in Scheme 3. In comparison to a zip‐fastener or zipper this reaction is called “zipreaction”.