title: The Total Synthesis of Starfish Ganglioside GP3 Bearing a Unique Sialyl Glycan Architecture.
abstract: The total synthesis of ganglioside GP3, which is found in the starfish Asterina pectinifera, has been accomplished through stereoselective and effective glycosylation reactions. The sialic acid embedded octasaccharide moiety of the target compound was constructed by [4+4] convergent coupling. A tetrasaccharyl donor and acceptor that contained internal sialic acid residues were synthesized with an orthogonally protected N-Troc sialic acid donor as the key common synthetic unit, and they underwent highly stereoselective glycosidation. The resulting sialosides were subsequently transformed into reactive glycosyl acceptors. [4+4] coupling furnished the octasaccharide framework in 91 % yield as a single stereoisomer. Final conjugation of the octasaccharyl donor and glucosyl ceramide acceptor produced the protected target compound in high yield, which underwent global deprotection to successfully deliver ganglioside GP3.
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax.
authors.forename: Kenta
authors.initials: K
authors.lastname: Goto
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax.
authors.forename: Maki
authors.initials: M
authors.lastname: Sawa
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax.|Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Hideki
authors.initials: H
authors.lastname: Tamai
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Imamura
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax. hando@gifu-u.ac.jp.|Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto, 606-8501, Japan. hando@gifu-u.ac.jp.
authors.forename: Hiromune
authors.identifier: 0000-0002-0551-0830
authors.initials: H
authors.lastname: Ando
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax.
authors.forename: Hideharu
authors.initials: H
authors.lastname: Ishida
authors.affiliation: Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu-shi, Gifu, 501-1193, Japan), Fax. kiso@gifu-u.ac.jp.|Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto, 606-8501, Japan. kiso@gifu-u.ac.jp.
authors.forename: Makoto
authors.initials: M
authors.lastname: Kiso
mesh_terms: D000818:Animals; D005732:Gangliosides / Q000138:chemical synthesis* / Q000737:chemistry*; D006031:Glycosylation; D012794:Sialic Acids / Q000737:chemistry*; D013215:Starfish / Q000737:chemistry* / Q000378:metabolism; D013237:Stereoisomerism
chemical_list: D005732:Gangliosides; D012794:Sialic Acids
keywords: ganglioside; glycosylation; sialic acid; starfish; total synthesis