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Synthesis of Gabosine A and N from Ribose by the Use of Ring‐Closing Metathesis
Author(s) -
Monrad Rune Nygaard,
Fanefjord Mette,
Hansen Flemming Gundorph,
Jensen N. Michael E.,
Madsen Robert
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800983
Subject(s) - chemistry , ring closing metathesis , total synthesis , metathesis , tandem , salt metathesis reaction , aldehyde , bromide , diene , ring (chemistry) , stereochemistry , olefin fiber , ribose , medicinal chemistry , organic chemistry , catalysis , materials science , natural rubber , composite material , polymerization , enzyme , polymer
A concise synthetic route is described for the synthesis of gabosine A and N. The key step uses a zinc‐mediated tandem reaction where methyl 5‐deoxy‐5‐iodo‐2,3‐ O ‐isopropylidene‐β‐ D ‐ribofuranoside is fragmented to give an unsaturated aldehyde which is allylated in the same pot with 3‐benzoyloxy‐2‐methylallyl bromide. The functionalized octa‐1,7‐diene, thus obtained, is converted into the six‐membered gabosine skeleton by ring‐closing olefin metathesis. Subsequent protective group manipulations and oxidation gives rise to gabosine N in a total of 8 steps from ribose while the synthesis of gabosine A employs an additional step for inverting a secondary hydroxy group. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)