Addition of malonyl radicals to glycals with C-1 acceptor groups: remarkable influence of the substituents on the product distribution.
The ceric(IV) ammonium nitrate (CAN)-mediated radical addition of dimethyl malonate to glycals 1 affords methyl glycosides 2 and ortho esters 3 as main products; the product distribution strongly depends on the substitution pattern at the 1-position, which can be rationalized in terms of the oxidation potentials of the intermediary anomeric radicals.
Department of Organic Chemistry, University of Debrecen, PO Box 20, H-4010 Debrecen, Hungary.
Viktor
V
Gyóllai
Dirk
D
Schanzenbach
László
L
Somsák
Torsten
T
Linker
D002384:Catalysis; D002563:Cerium; D005690:Galactose / Q000031:analogs & derivatives* / Q000737:chemistry; D006027:Glycosides / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008314:Malonates / Q000737:chemistry*; D009005:Monosaccharides / Q000737:chemistry*; D010084:Oxidation-Reduction
D006027:Glycosides; D007202:Indicators and Reagents; D008314:Malonates; D009005:Monosaccharides; C002038:galactal; D002563:Cerium; C004653:ceric ammonium nitrate; D005690:Galactose