ChemInform Abstract: Asymmetric C-N Bond Constructions via Crotylsilane Addition Reactions: A Stereocontrolled Route to Dipeptide Isosteres.

✍ Scribed by C. E. MASSE; B. S. KNIGHT; P. STAVROPOULOS; J. S. PANEK

• Publisher: John Wiley and Sons
• Year: 2010
• Weight: 32 KB
• Volume: 28
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.199742243

✦ Synopsis

Asymmetric C-N Bond Constructions via Crotylsilane Addition

Reactions: A Stereocontrolled Route to Dipeptide Isosteres.

-A new, general, highly diastereo-and enantiospecific method for the asymmetric synthesis of (E)-olefin dipeptide isosteres is described. It involves the addition of chiral (E)-crotylsilanes to nitrogen-based electrophiles. The asymmetric C-N bond construction results from nitronium tetrafluoroborate promoted electrophilic nitrations of the chiral silanes and from a copper(I)-catalyzed enantioselective aziridination of the silane. The (E)-olefin isosteres are nonhydrolyzable, rigid analogues of the peptide linkage in biologically active peptides.