Novel glycosidation method using 2,6-anhydro-2-thio sugars for stereocontrolled synthesis of 2,6-dideoxy-α- and -β-glycosides

Kazunobu Toshima, Satsuki Mukaiyama, Yuko Nozaki, Hatsuki Inokuchi, Masaya Nakata, Kuniaki Tatsuta

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Powerful and highly stereocontrolled O-glycosidation methods using several kinds of 2,6-anhydro-2-thio sugars as glycosyl donors have been developed for the synthesis of both 2,6-dideoxy-α- and -β-glycosides which frequently occur in biologically important natural products. Both glycosidations of phenyl 3,4-di-O-acetyl-2,6-anhydro-1,2-dithio-D-altropyranoside (2) and 3,4-di-O-acetyl-2,6-anhydro-1-fluoro-2-thio-D-altropyranoside (3) with alcohols exclusively gave the corresponding 2,6-anhydro-2-thio-α-glycosides. In contrast, the glycosidations of 1,3,4-tri-O-acetyl-2,6-anhydro-2-thio-D-altropyranose (4) with alcohols afforded the corresponding 2,6-anhydro-2-thio-β-glycosides with high stereocontrol. Furthermore, a novel method for the controlled block synthesis of 2,6-dideoxy oligosaccharides by the combined use of the activated 2,6-anhydro-2-thio sugar 23 and the deactivated 2,6-anhydro-2-sulfinyl sugar 24, both of which have the same thiophenyl leaving group at the anomeric positions, has been demonstrated. The 2,6-anhydro-2-thio-α- and -β-glycosides obtained by the present methods were effectively converted into the corresponding 2,6-dideoxy-α- and -β-glycosides by both hydrogenolysis using Raney-Ni as a catalyst and reductive desulfurization using Bu3SnH and AIBN.

Original languageEnglish
Pages (from-to)9042-9051
Number of pages10
JournalJournal of the American Chemical Society
Volume116
Issue number20
DOIs
Publication statusPublished - 1994 Oct 5

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Thiosugars
Glycosides
Sugars
Alcohols
Oligosaccharides
Hydrogenolysis
2,4-Dichlorophenoxyacetic Acid
Desulfurization
Biological Products
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

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Novel glycosidation method using 2,6-anhydro-2-thio sugars for stereocontrolled synthesis of 2,6-dideoxy-α- and -β-glycosides. / Toshima, Kazunobu; Mukaiyama, Satsuki; Nozaki, Yuko; Inokuchi, Hatsuki; Nakata, Masaya; Tatsuta, Kuniaki.

In: Journal of the American Chemical Society, Vol. 116, No. 20, 05.10.1994, p. 9042-9051.

Research output: Contribution to journalArticle

Toshima, Kazunobu ; Mukaiyama, Satsuki ; Nozaki, Yuko ; Inokuchi, Hatsuki ; Nakata, Masaya ; Tatsuta, Kuniaki. / Novel glycosidation method using 2,6-anhydro-2-thio sugars for stereocontrolled synthesis of 2,6-dideoxy-α- and -β-glycosides. In: Journal of the American Chemical Society. 1994 ; Vol. 116, No. 20. pp. 9042-9051.
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abstract = "Powerful and highly stereocontrolled O-glycosidation methods using several kinds of 2,6-anhydro-2-thio sugars as glycosyl donors have been developed for the synthesis of both 2,6-dideoxy-α- and -β-glycosides which frequently occur in biologically important natural products. Both glycosidations of phenyl 3,4-di-O-acetyl-2,6-anhydro-1,2-dithio-D-altropyranoside (2) and 3,4-di-O-acetyl-2,6-anhydro-1-fluoro-2-thio-D-altropyranoside (3) with alcohols exclusively gave the corresponding 2,6-anhydro-2-thio-α-glycosides. In contrast, the glycosidations of 1,3,4-tri-O-acetyl-2,6-anhydro-2-thio-D-altropyranose (4) with alcohols afforded the corresponding 2,6-anhydro-2-thio-β-glycosides with high stereocontrol. Furthermore, a novel method for the controlled block synthesis of 2,6-dideoxy oligosaccharides by the combined use of the activated 2,6-anhydro-2-thio sugar 23 and the deactivated 2,6-anhydro-2-sulfinyl sugar 24, both of which have the same thiophenyl leaving group at the anomeric positions, has been demonstrated. The 2,6-anhydro-2-thio-α- and -β-glycosides obtained by the present methods were effectively converted into the corresponding 2,6-dideoxy-α- and -β-glycosides by both hydrogenolysis using Raney-Ni as a catalyst and reductive desulfurization using Bu3SnH and AIBN.",
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AB - Powerful and highly stereocontrolled O-glycosidation methods using several kinds of 2,6-anhydro-2-thio sugars as glycosyl donors have been developed for the synthesis of both 2,6-dideoxy-α- and -β-glycosides which frequently occur in biologically important natural products. Both glycosidations of phenyl 3,4-di-O-acetyl-2,6-anhydro-1,2-dithio-D-altropyranoside (2) and 3,4-di-O-acetyl-2,6-anhydro-1-fluoro-2-thio-D-altropyranoside (3) with alcohols exclusively gave the corresponding 2,6-anhydro-2-thio-α-glycosides. In contrast, the glycosidations of 1,3,4-tri-O-acetyl-2,6-anhydro-2-thio-D-altropyranose (4) with alcohols afforded the corresponding 2,6-anhydro-2-thio-β-glycosides with high stereocontrol. Furthermore, a novel method for the controlled block synthesis of 2,6-dideoxy oligosaccharides by the combined use of the activated 2,6-anhydro-2-thio sugar 23 and the deactivated 2,6-anhydro-2-sulfinyl sugar 24, both of which have the same thiophenyl leaving group at the anomeric positions, has been demonstrated. The 2,6-anhydro-2-thio-α- and -β-glycosides obtained by the present methods were effectively converted into the corresponding 2,6-dideoxy-α- and -β-glycosides by both hydrogenolysis using Raney-Ni as a catalyst and reductive desulfurization using Bu3SnH and AIBN.

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