title: 6-Azido-6-deoxy-l-idose as a Hetero-Bifunctional Spacer for the Synthesis of Azido-Containing Chemical Probes.
abstract: The design of 6-azido-6-deoxy-l-idose for use as a hetero-bifunctional spacer is reported. The hemiacetal at one terminus is an equivalent of an aldehyde and can react with nucleophiles, such as amino groups and electron-rich aromatics. The azido group at the other terminus bio-orthogonally undergoes a Hüisgen [3+2] cycloaddition with an acetylene. The idose derivative exhibited a higher level of reactivity towards oxime formation than a corresponding glucose derivative. The (13) C NMR spectrum of the uniformly (13) C-labeled 6-azido-idose indicated that the acyclic forms of the sugar totaled 0.3 % of all the isomers, whereas those of glucose totaled 0.01 %. The larger population of the acyclic forms of the idose derivative would result in higher reactivity towards electrophilic addition in comparison with glucose derivatives. Finally, we prepared a C-idosyl epigallocatechin gallate (EGCG) that bears an azido group through C-glycosylation of EGCG with 6-azido-idose. This glycosyl form of the C-idosyl EGCG exhibited a cytotoxicity against U266 cells that was comparable to that of EGCG. These results suggested that the EGCG derivative could be used as an effective chemical probe for the elucidation of EGCG biological functions.
authors.affiliation: Department of Chemical Science and Engineering, School of Material and Chemical Technology, Tokyo Institute of Technology, 2-12-1-H101 Ookayama, Meguro, Tokyo, 152-8552, Japan.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Hamagami
authors.affiliation: Department of Bioscience and Biotechnology, Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Fukuoka, 812-8581, Japan.
authors.forename: Motofumi
authors.initials: M
authors.lastname: Kumazoe
authors.affiliation: RIKEN-Max-Planck Joint Research Center, for Systems Chemical Biology, RIKEN Global Research Cluster, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
authors.forename: Yoshiki
authors.initials: Y
authors.lastname: Yamaguchi
authors.affiliation: Department of Chemical Science and Engineering, School of Material and Chemical Technology, Tokyo Institute of Technology, 2-12-1-H101 Ookayama, Meguro, Tokyo, 152-8552, Japan.|Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Shinichiro
authors.initials: S
authors.lastname: Fuse
authors.affiliation: Department of Bioscience and Biotechnology, Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Fukuoka, 812-8581, Japan.
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Tachibana
authors.affiliation: Department of Chemical Science and Engineering, School of Material and Chemical Technology, Tokyo Institute of Technology, 2-12-1-H101 Ookayama, Meguro, Tokyo, 152-8552, Japan. thiroshi@apc.titech.ac.jp.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Tanaka
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D002392:Catechin / Q000031:analogs & derivatives* / Q000737:chemistry; D003837:Deoxy Sugars / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D006031:Glycosylation; D006601:Hexoses / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy
chemical_list: C438083:6-deoxy-idose; D000447:Aldehydes; D001386:Azides; D003837:Deoxy Sugars; D006601:Hexoses; D002392:Catechin; C045651:epigallocatechin gallate; D005947:Glucose
keywords: C-glycosylation; Lewis acids; aldehydes; oximes; phytochemistry