Photo amidoglycosylation of an allal azidoformate. Synthesis of beta-2-amido allopyranosides.
[figure: see text] Photolysis of an allal C-3 azidoformate provoked intramolecular nitrene insertion into the glycal C=C unit and allowed direct incorporation of alcohol nucleophiles as beta-disposed substituents at C-1. The 2-amido allopyranoside products were elaborated via N-acylation and selective oxazolidinone hydrolysis, providing N-Boc-protected 2-amino sugars and simplifying stereochemical assignments. Synthesis of the potentially labile allal azidoformate was achieved via reaction of the corresponding carbonyl imidazolide with trimethylsilyl azide, facilitated by dibutyltin oxide.
Kan
C
C
Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA.
Long
C M
CM
Paul
M
M
Ring
C M
CM
Tully
S E
SE
Rojas
C M
CM
D000577:Amides / Q000737:chemistry; D001386:Azides / Q000737:chemistry; D002236:Carbohydrate Conformation; D005561:Formates / Q000737:chemistry; D006027:Glycosides / Q000138:chemical synthesis*; D006031:Glycosylation; D010782:Photolysis
D000577:Amides; D001386:Azides; D005561:Formates; D006027:Glycosides