title: D-Glucosamine-derived synthons for assembly of L-threo-sphingoid bases. Total synthesis of rhizochalinin C.
abstract: A five-step transformation of D-glucosamine, commencing with indium-mediated Barbier reaction without isolation of intermediates, into (R,R)-2-aminohex-5-ene-1,3-diol in 45-51% is described. The latter is a useful synthon for assembly of L-threo-sphingoid bases: long-chain aminoalkanols and aminoalkanediols with configurations antipodal to that found in mammalian D-erythro-sphingosine but prevalent among invertebrate-derived sphingolipids. The utility of the method is demonstrated by the first total synthesis of rhizochalinin C, the long-chain, "two-headed" sphingoid base aglycon of the natural product rhizochalin C from the marine sponge Rhizochalina incrustata.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, USA.
authors.forename: Jaeyoung
authors.initials: J
authors.lastname: Ko
authors.forename: Tadeusz F
authors.initials: TF
authors.lastname: Molinski
mesh_terms: D001688:Biological Products / Q000737:chemistry*; D005944:Glucosamine / Q000737:chemistry*; D006028:Glycosphingolipids / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D012232:Rhizoctonia / Q000737:chemistry*; D013110:Sphingosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D001688:Biological Products; D006028:Glycosphingolipids; C481931:erythro-(2R,3S)-sphingosine; C527012:rhizochalin C; D005944:Glucosamine; D013110:Sphingosine