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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Stereoselective ring contractions in glycopyranosides as key-step en route to isoiminosugars
Alexander Luttenberger1, Elena Spari1, André Culum1
1Graz University of Technology, Institute of Chemistry and Technology of Biobased Systems, Stremayrgasse 9, A-8010, Graz, Austria.
Abstract:
Isoiminosugars are glycomimetics and selective and highly potent inhibitors for glycoside hydrolases. Their structural characteristics still remain a challenge and show the need for efficient synthetic approaches when compared to similar more easily available relatives. Herein, we provide a general synthetic concept for advanced derivatives of this compound class. A LiAlH4 induced stereoselective 1,2-shift of C-4 to C-2 in O-2 tosylated d-glucopyranosides leading to ring-contracted C-2 branched d-ribofuranosides allows for convenient access to either C-2- or C-5a-elongated analogues of powerful β-galactosidase inhibitor 4-epi-isofagomine. Mechanistic insights into the synthetic key-step, as well as its broader application targeting d-gluco mimicking isoiminosugars are provided.
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