Abstract
C-Allylglycyl amides can be efficiently synthesized via an auxiliary controlled diastereoselective
aza-Claisen rearrangement. The stereodirecting unit is placed on an auxiliary derived
from commercially available (S)-proline. After N-allylation, the obtained optically active allylamines were reacted
with various N-protected glycyl fluorides to give the (2R)-C-allylglycyl amides in good yields. The diastereoselectivity of the asymmetric allylation
varied between 1:1 and >1:15 depending on the N-protective group, the auxiliary, and the reaction temperature. Likewise, the C-allyl-glycine derivatives can be used as monomers in peptide synthesis to synthesize
(R)-proline derivatives or chiral isoquinolones; the latter should serve as building
blocks in the total syntheses of alkaloids.
Key words
chiral auxiliaries - amino acids - isoquinolone - allylations - aza-Claisen rearrangement
- stereoselective synthesis
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