Diastereoselective access to C , C -glycosyl amino acids via iron-catalyzed, auxiliary-enabled MHAT coupling.

Access to C , C -glycosyl amino acids as a novel class of glycomimetics is reported by means of radical generation, intermolecular addition and stereoselective reduction via a metal-induced hydrogen atom transfer (MHAT) sequence. The 'matched' coupling of exo -D-glycals with an enantiopure dehydroalanine bearing a ( R )-configured benzyl oxazolidinone enables a singular case of two-fold diastereocontrol under iron catalysis. In the common exo -D-glucal series, the nature of the C-2 substituent was found to play a key role from both reactivity and stereocontrol aspects.