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Synthesis of 1-Deoxymannojirimycin from d-Fructose using the Mitsunobu Reaction
Peter Sunde-Brown1, Ian D Jenkins2, Todd A Houston1,3
1Institute for Glycomics, Griffith University, Gold Coast Campus, Southport 4215, QLD, Australia.
Abstract:
Three different Mitsunobu reactions have been investigated for the synthesis of 1-deoxymannojirimycin (1-DMJ) from d-fructose. The highest yielding and most practical synthesis can be undertaken on a 10 g scale with minimal chromatography. In the key step, N,O-di-Boc-hydroxylamine reacts with methyl 1,3-isopropylidene-α-d-fructofuranose under Mitsunobu conditions to give 14. Acidic hydrolysis affords nitrone 15, which reduces quantitatively via catalytic hydrogenolysis to afford 1-DMJ (4) in 55% overall yield from d-fructose (cf. 37% for azide route and 29% for nosyl route).
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