Synthesis of E-vinylogous ( R)-amino acid derivatives via metal-catalyzed allylic substitutions on enzyme-derived substrates

[Display omitted] Oxynitrilase-derived allylic ( R)-cyanohydrin carbonates 3 and allylic ( R)-α-hydroxy ester carbonates 6 were examined as substrates for a palladium(0)-catalyzed allylic azidation reaction. The enantioselectivities and cis/trans diastereoselectivities of the concomitant 1,3-chirali...

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Published in:Tetrahedron: asymmetry 2005-05, Vol.16 (9), p.1655-1661
Main Authors: Deardorff, Donald R., Taniguchi, Cullen M., Nelson, Anna C., Pace, Andrew P., Kim, Alexander J., Pace, Aaron K., Jones, Regan A., Tafti, Sanaz A., Nguyen, Charles, O’Connor, Caitlin, Tang, Judy, Chen, Judy
Format: Article
Language:English
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Summary:[Display omitted] Oxynitrilase-derived allylic ( R)-cyanohydrin carbonates 3 and allylic ( R)-α-hydroxy ester carbonates 6 were examined as substrates for a palladium(0)-catalyzed allylic azidation reaction. The enantioselectivities and cis/trans diastereoselectivities of the concomitant 1,3-chirality transposition step were studied. The cyano carbonates 3a– c were found to be unimpressive substrates producing γ-azido-α,β-unsaturated nitriles 4a– c with cis/trans ratios that approached unity and gave enantiomeric excesses that ranged from 57% to 85%. In contrast, ester carbonates 6a and b were excellent substrates for the reaction exclusively affording trans substitution products 7a and b in identical enantiomeric excesses of 95% ee.
ISSN:0957-4166
1362-511X
DOI:10.1016/j.tetasy.2005.03.018