Synthesis of C-Glycosyl Compounds. Part 1.ˡ Reaction of Ethyl Isocyanoacetate with 2,3:5,6-Di-O-Isopropylidene-D-Mannono-1,4-Lactone

Abstract

Formylaminomethylenation of 2,3:5,6-Di-O-Isopropylidene-D-Mannono-L,4-Lactone (1) with Ethyl Isocyanoacetate (2) Gave, as the Major Product, (E)-Ethyl 3,6-Anhydro-2-Deoxy-2-Formylamino-4,5:7,8-Di-O-Isopropylidene-D-Manno-Oct-2-Enonate (3) (58%). Which on Hydrogenation Gave Ethyl 3.6-Anhydr0-2-Deoxy-2-Formylamino- 4.5:7,8-Di-0-Isopropylidene-D-Eryfhro-L-Gluco-Octonate (17). in Almost Quantitative Yield. Base-Catalysed Equilibration of the D-Eryfhro-L-Gho-Octonate (17) Gave a Mixture of the L-Allo-, L-Alfro-, L-Gluco-, and L-Mannoepimers [(23), (22). (17). and (19). Respectively]. the Configurations at C-2 and C-3 of These Epimers Were Established by Chemical and Physical Methods. the D-Eryfhro-L-Gluco-Epimer (17) and the D- Erythro -L-Manno-Epimer (19) Were Degraded to Ethyl 3.6-Anhydro-2-Deoxy-2-Informylamino-4,5-O– Isopropylidene-D-Glycero-L-Gluco-Heptonate(37) and its D -Glycero - L-Mannoepimer (39), Respectively. Acidic Hydrolysis of Compounds (17). (19). (37), and (39) Gave the Free Amino-Acids, L-2-(P-D-Mannofuranosyt) -Glycine (41), the Analogous D-Amino-Acid (42). L-2-(Β-D-Tyxofuranosyl)-Gtycin(43). and the Analogous D-Amino-Acid (44). in Moderate Yields. in the Presence of Base, Alcohols and Thiols Readily Attacked the Double Bond of the Oct-2-Enonate (3) to Give, for Example, Ethyl (Ethyl2-Deoxy-2-Formylamino-4,5:7,8-Di-O-Isopropylide-Α-D-Manno-D-Glycero-Oct-3-Ulo-3.6-Furanosid)onate and its D-Manno-L-Glycefo-Epimer [(9) and (10)]. © 1977, Royal Society of Chemistry.

Department(s)

Business and Information Technology

International Standard Serial Number (ISSN)

1470-4358

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2023 Royal Society of Chemisttry, All rights reserved.

Publication Date

01 Jan 1977

Link to Full Text

Share

 
COinS