A route to 1-Deoxynojirimycin and 1-Deoxymannojirimycin derivatives with quaternary centers adjacent to the ring nitrogen from Methyl α-d-Mannopyranoside
Chadda, Rekha Murphy, Paul V.
Chadda, Rekha
Murphy, Paul V.
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Publication Date
2020-02-03
Type
Article
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Citation
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
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.
Publisher
Wiley
Publisher DOI
10.1002/ejoc.201901875
Rights
CC BY-NC-ND 3.0 IE