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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Synthesis of spirocyclic C-arylglycosides and -ribosides by ruthenium-catalyzed cycloaddition
Yoshihiko Yamamoto1, Ken Yamashita, Tomitaka Hotta
1Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan. omyy@apc.titech.ac.jp
Abstract:
Spirocyclic C-arylglycosides were synthesized from the appropriately protected delta-gluconolactones. Addition of lithium acetylide followed by glycosylation with 3-(trimethylsilyl)propargyl alcohol converted the delta-gluconolactones into silylated diynes. After desilylation, subsequent ruthenium-catalyzed cycloaddition of the resultant diynes with alkynes or chloroacetonitrile gave spirocyclic C-arylglycosides in good yields and selectivity. This strategy was also extended to the synthesis of spirocyclic C-arylribosides from the known gamma-ribonolactone derivative. Moreover, silver-catalyzed iodination of the sugar diynes followed by ruthenium-catalyzed cycloaddition with acetylene delivered spirocyclic C-iodophenylglycosides and -ribosides, which were subjected to palladium-catalyzed C-C bond-forming reactions and copper-catalyzed coupling with nitrogen heterocycles to lead to various derivatives.
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