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Permanganate Oxidation Revisited: Synthesis of 3‐Deoxy‐2‐uloses via Indium‐Mediated Chain Elongation of Carbohydrates
Author(s) -
Schmölzer Christoph,
Fischer Michael,
Schmid Walther
Publication year - 2010
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.201000623
Subject(s) - chemistry , moiety , potassium permanganate , combinatorial chemistry , molecule , olefin fiber , stereochemistry , alkene , permanganate , organic chemistry , catalysis
Application of the Barbier‐type indium‐mediated allylation method to suitable substrates offers access to carbohydrates bearing a terminal olefin moiety. The C–C bond forming reaction generates a defined stereochemistry of the new chiral center and tolerates a wide variety of starting aldehydes thus allowing modifications in the carbohydrate backbone. Further transformations of the alkene moiety via an environmentally benign and subtle controlled protocol using potassium permanganate gives rise to the structural motif of 3‐deoxy‐2‐uloses in good yields. The final part of the reaction sequence focuses on the deprotection of the acetyl groups essential for the success of the oxidation step. The acidic and labile 3‐deoxy position of the target molecule is prone to elimination applying standard deacetylation conditions and therefore demands derivatisation of the molecule. The introduction of a thioketal moiety using microwave conditions shows promising results and subsequent standard transformations are applicable leading to the desired products.