A route to 1-Deoxynojirimycin and 1-Deoxymannojirimycin derivatives with quaternary centers adjacent to the ring nitrogen from Methyl α-d-Mannopyranoside
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2020-02-03Author
Chadda, Rekha
Murphy, Paul V.
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Chadda, Rekha, & Murphy, Paul V. (2020). A Route to 1-Deoxynojirimycin and 1-Deoxymannojirimycin Derivatives with Quaternary Centers Adjacent to the Ring Nitrogen from Methyl α-d-Mannopyranoside. European Journal of Organic Chemistry, 2020(16), 2389-2398. doi: https://doi.org/10.1002/ejoc.201901875
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Abstract
6-Alkylated-8-azido-1,6-octadiene derivatives were prepared from methyl α-D-mannopyranoside. The
sequence to allylic azide precursors included a Horner-Wadsworth-Emmons reaction with a concomitant
epimerization that ultimately enabled synthesis of 1-deoxynojirimycin as well as 1-deoxymannojirimy-
cin derivatives. Thermally promoted allylic acid rearrangement followed by triazoline formation, then
decomposition to aziridine and finally reaction with acetic acid was used to generate products that have
quaternary anomeric centers adjacent to the piperidine ring nitrogen atom (cyclic α-tertiary amines).
The stereoselectivity is accounted for based on minimization of steric interactions in the transition state
structure, favouring the product where the larger methyl substituent is equatorial and the vinyl group
prefers to be axial.