A Novel 2H-Azirin-3-amine as a Dipeptide (Aib-Hyp) Synthon

✍ Scribed by Roland A. Breitenmoser; Thomas R. Hirt; Roeland T. N. Luykx; Heinz Heimgartner

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: German
• Weight: 104 KB
• Volume: 84
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/1522-2675(20010418)84:4<972::aid-hlca972>3.0.co;2-m

✦ Synopsis

The synthesis of methyl (2S,4R)-4-(benzyloxy)-N-(2,2-dimethyl-2H-azirin-3-yl)prolinate ( 10), a novel 2Hazirin-3-amine (3-amino-2H-azirine), is described (Scheme 1). The reaction of methyl (2S,4R)-N-(2methylpropanoyl)-4-(benzyloxy)prolinate ( 7) with Lawesson reagent gave methyl (2S,4R)-4-(benzyloxy)-N-[2-(methylthio)propanoyl]prolinate (8) and consecutive treatment with COCl 2 , 1,4-diazabicyclo[2.2.2]octane (DABCO), and NaN 3 led to 10. The use of 10 as a building block of the dipeptide Aib-Hyp (Aib 2aminoisobutyric acid, Hyp (2S,4R)-4-hydroxyproline) is demonstrated by the syntheses of several model peptides (Scheme 2 and Table ). The benzyl protecting group of the 4-OH function in Hyp in the model peptides has been removed in good yields.