New building blocks for iminosugars: a concise synthesis of polyhydroxylated N-alkoxypiperidines through an intramolecular azepine ring contraction. Issue 5 (24th March 2015)

• Record Type: Journal Article
• Authors: Barnes, Korry L.; Chen, Kelly; Catalano, Vincent J.; Jeffrey, Christopher S.
• Is Part Of: Organic chemistry frontiers. Volume 2:Issue 5(2015:May.)
• Page Start: 497
• Page End: 501
• Publication Date: 2015-03-24
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/c4qo00330f
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : Polyhydroxylated piperidines are a functionally rich class of biologically active molecules that have broad therapeutic potential. Abstract : Polyhydroxylated piperidines are a functionally rich class of biologically active molecules that have broad therapeutic potential. Recently developed aza-[4 + 3] cycloadditions of putative aza-oxyallylic cations provide heterocyclic scaffolds that enabled a concise synthesis of polyhydoxylated piperidines. Chemoselective amide reduction and reductive hemiaminal ring opening was achieved in one pot by the action of aluminium hydride generated in situ via aluminium chloride and lithium aluminium hydride. Aziridinium ion mediated ring contraction and chloride displacement was triggered by silver acetate, followed by simple acetate hydrolysis using potassium carbonate to give four tetrahydropyridine diols. Olefin oxidation by osmium tetroxide installed the final hydroxyl groups, which yielded four novel polyhydroxylated N -alkoxypiperidines in good overall yield and high diastereoselectivity.