Convenient Syntheses and Transformations of 2‐ C ‐Malonyl Carbohydrates

2‐ C ‐malonyl carbohydrates were synthesized in only few steps and high yields by radical additions of malonates to glycals. For the first time, the undesired formation of nitrates was completely suppressed with anhydrous cerium ammonium nitrate (CAN) as oxidizing agent. A coherent explanation for the high stereoselectivities of the additions to gluco ‐configured glycals was provided by variation of the substituents in the 3‐position. We established steric effects for the face selectivity, and electronic effects strongly influence the reactivity of the double bonds. The scope and limitation of transition‐metal‐mediated radical reactions in the synthesis of 2‐ C ‐branched carbohydrates was thoroughly investigated. Thus, unsaturated disaccharides and benzyl‐protected glycals were used as substrates for the first time. Finally, the 2‐ C ‐malonyl carbohydrates were transformed into various products by decarboxylation, saponification and reduction, which afforded interesting precursors for C ‐disaccharides. In this paper we describe the syntheses of more than 40 new 2‐ C ‐analogues of carbohydrates, which were isolated in high yields in analytically pure form. Therefore, the transition‐metal‐mediated radical addition of malonates to glycals offers a simple and convenient entry to such important carbohydrate derivatives.