title: Stereospecific generation and analysis of α- and β-hemiacetals of monosaccharides in gas phase.
abstract: A series of Boc-protected 4-aminobutyl α- and β-glycosides of commonly found neutral monosaccharides were synthesized. The sodium adducted ions of these individual molecules were used in producing corresponding α- and β-anomers of hemiacetal species under collision-induced dissociation (CID) conditions. The Boc group was successfully removed under CID conditions producing 4-aminobutyl glycosides, which were then used as the precursors. An intramolecular attack of the aglyconic nitrogen atom onto C-1 position of aglycon assisted to leave hemiacetal ion species without affecting anomeric configurations. In this manner, stereospecific syntheses of sugar hemiacetals were first achieved in gas phase. The dissociation of sodium cation from a series of these hemiacetals was further studied according to energy-resolved mass spectrometry. In this study, it was found that all the sugar hemiacetals could be distinguished even if they have same m/z values. Furthermore, the order of affinity of Na(+) toward the hemiacetals was determined.
authors.affiliation: Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4529 Nagatsuta-cho, Midori-ku, Yokohama 226-0018, Japan; Synthetic Cellular Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Shioiri
authors.forename: Katsuhiko
authors.initials: K
authors.lastname: Suzuki
authors.forename: Shusaku
authors.initials: S
authors.lastname: Daikoku
authors.forename: Ayako
authors.initials: A
authors.lastname: Kurimoto
authors.forename: Yukishige
authors.initials: Y
authors.lastname: Ito
authors.forename: Osamu
authors.initials: O
authors.lastname: Kanie
mesh_terms: D000080:Acetals / Q000138:chemical synthesis / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D005740:Gases / Q000737:chemistry; D013058:Mass Spectrometry; D009005:Monosaccharides / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000080:Acetals; D005740:Gases; D009005:Monosaccharides; D012964:Sodium
keywords: Anomeric configurations; Collision-induced dissociation; Energy-resolved mass spectrometry; HOLZDXDNROHPOP-CLACGNGHSA-N; HOLZDXDNROHPOP-MMCPYJTDSA-N; HOLZDXDNROHPOP-ODGNXRKOSA-N; HOLZDXDNROHPOP-PCGVCOGMSA-N; Hemiacetals; Monosaccharides; OVRNDRQMDRJTHS-BCHXKHGJSA-N; OVRNDRQMDRJTHS-SHWWSFLJSA-N; OVRNDRQMDRJTHS-VCIONDPNSA-N; OVRNDRQMDRJTHS-VWVVONKMSA-N; RAKUMWASVULGKS-APSDNXJZSA-N; RAKUMWASVULGKS-DRYUAMBJSA-N; RAKUMWASVULGKS-IJTJVXSJSA-N; RAKUMWASVULGKS-XNYRDIBGSA-N; SHZGCJCMOBCMKK-AMXSVAROSA-N; SHZGCJCMOBCMKK-SADXIQTQSA-N; SRBFZHDQGSBBOR-UOFNXBMGSA-N; SRBFZHDQGSBBOR-YQWWZGPCSA-N; VPVVPIYSTJLUAP-LSBUWSJDSA-N; VPVVPIYSTJLUAP-ZWMSFMBMSA-N; WQZGKKKJIJFFOK-DLGJCNIVSA-N; WQZGKKKJIJFFOK-DTUOTYQVSA-N; WQZGKKKJIJFFOK-KYKSVUQTSA-N; WQZGKKKJIJFFOK-OOMLUFPTSA-N; YFJHWEQHVCSSTI-AIROJPCNSA-N; YFJHWEQHVCSSTI-AYLPWXGPSA-N