C‐Glycosidations of a 2‐Ketohexosyl Bromide with Electrophilic, Radical, and Nucleophilic Anomeric Carbons

Abstract

AbstractThe susceptibility of acylated 2‐ketohexosyl halides to C‐homologation is demonstrated with the easily accessible tri‐O‐benzoyl‐α‐D‐arabino‐hexos‐ulosyl bromide 1 as the model compound. C‐Glycosidation with an electrophilic anomeric carbon requires prior carbonyl protection, to avoid carbonyl addition by the C‐nucleophile, for example, as the cyanohydrin. Silver triflate‐promoted reaction with the silylenol ether of acetophenone then efficiently yields the β‐phenacyl product. With thermal (AIBN) or photochemical induction, 1 smoothly generates an anomeric radical − comparatively electrophilic, due to its capto‐dative substitution − which exclusively traps hydrogen in the presence of tributyltin and electron‐deficient alkenes. With allyltributylstannanes, however, it reacts with high stereoselectivity to afford α‐C‐allyl glycosiduloses. The α‐bromoketone functionality in ulosyl bromide 1 is susceptible to Reformatsky conditions: treatment with zinc‐copper couple readily generates the 1,2‐enolate, a most simple anomeric nucleophile, which effectively adds to aldehydes to give α‐C‐hydroxyalkyl glycosiduloses or α‐C‐disaccharides (with sugar aldehydes) with a high degree of double stereoselection. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)