Addition of malonyl radicals to glycals with C-1 acceptor groups: remarkable influence of the substituents on the product distributionElectronic supplementary information (ESI) available: NMR data for C-2 branched sugar derivatives. See http://www.rsc.org/suppdata/cc/b2/b202898k/

Abstract

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.