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Stereospecific Synthesis of Glycoside Mimics Through Migita‐Kosugi‐Stille Cross‐Coupling Reactions of Chemically and Configurationally Stable 1‐ C ‐Tributylstannyl Iminosugars
Author(s) -
Li Sizhe,
Jaszczyk Justyna,
Pannecoucke Xavier,
Poisson Thomas,
Martin Olivier R.,
Nicolas Cyril
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000886
Subject(s) - stille reaction , chemistry , electrophile , iminosugar , stereospecificity , stereochemistry , stereoselectivity , anomer , glycosyl , coupling reaction , combinatorial chemistry , organic chemistry , catalysis , enzyme
Abstract A process for the de novo synthesis of imino‐ C ‐glycosides is described. The methodology is based on the reaction of 1‐C‐stannylated iminosugars with various electrophiles under the conditions of Migita‐Kosugi‐Stille cross‐couplings, which gives 1‐C‐substituted iminosugar derivatives in a stereoretentive process. The required iminoglycosyl stannanes are obtained by way of the highly stereoselective addition of tributylstannyllithium to ( S R )‐ or ( S S )‐ N ‐ tert ‐butanesulfinyl glycosylamines, followed by an activation cyclization sequence. Most interestingly, the methodology is tunable: the configuration of the tin adduct is controlled exclusively by the tert ‐butanesulfinyl auxiliary, thus giving access after ring formation to ‘α’‐configured or ‘β’‐configured iminoglycosyl stannanes. With the subsequent stereoretentive C−C bond‐forming process, the methodology allows the synthesis of pseudo anomers of imino‐ C ‐glycosyl compounds in a controlled fashion.