Cyano-Sugars. Part 3. Synthesis of 2-C-Cyano-2-Deoxy-Sugars from 2-C-Cyano-Galactals and Attempts to Prepare Pentofuranosyl Cyanides from Aldonic Acid Lactones with Tosylmethyl Isocyanide

Abstract

1,5-Anhydro-2-C-Cyano-2-Deoxy-D-Lyxo-Hex-1-Enitol (2) Reacted with Sodium Methoxide in Methanol to Give, after Acetylation, Methyl 3,4,6-Tri-O-Acetyl-2-C- Cyano-2-Deoxy-Β-D-Galactopyranoside (6) as the Main Product. Similar Treatment of 1,5-Anhydro-2-C-Cyano-2-Deoxy-1,2-O-Isopropylidene-D-Lyxo-Hex-1- Enitol (3) Gave Methyl 4,6-Di-O-Acetyl-2-C-Cyano-2-Deoxy-3-O-Methyl-Α-D- and -Β-D-Galactopyranoside (11) and (7), Respectively, as the Main Products. Compounds (6), (7), and (11) Were Converted into their 2-C-Acetamidomethyl Analogues (8), (9), and (12), Respectively, in High Yield by Catalytic Hydrogenation in Ethanol-Acetic Anhydride. the Formylaminomethylenation of 2,3:5,6-Di-O-Isopropylidene-D-Mannono-1,4-Lactone with Tosylmethyl Isocyanide Gave (E)- and (Z)-2,5-Anhydro-1-Deoxy-1-Formylamino- 3,4:6,7-Di-O-Isopropylidene-1-Tosyl-O-Manno-Hept-1-Enitol [(17) and (18)]. the Reaction of the Main Isomer (17) with 2 Equiv. of Sodium Ethoxide in Ethanol, Gave Ethyl [(1R)-O-Ethyl-1-Formylamino-3,4:6,7-Di-O-Isoproyplidene-Aldehydro- Α-D-Manno-Heptafuranos]uloside and its (1S)-Epimer [(21) and (22)], and Not 2,3:5,6-Di-O-Isopropylidene-Α,β-D-Mannofuranosyl Cyanide, as Expected. 2,3:5,6-Di-O-Isopropylidene-D-Gulono-1,4-Lactone Behaved Similarly.

Department(s)

Business and Information Technology

International Standard Serial Number (ISSN)

1472-7781

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2023 Royal Society of Chemistry, All rights reserved.

Publication Date

01 Jan 1979

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