Mechanism of Chemical Glycosylation: Focus on the Mode of Activation and Departure of Anomeric Leaving Groups

Automated Chemical Synthesis of Oligosaccharides and Glycoconjugates

“…Solution-based microreactors, developed in the late nineties, have been adapted to the fluorous tag-supported synthesis of oligosaccharides by Seeberger and co-workers [137]. A five-port silicon microfluidic reactor was utilized for the synthesis of the homotetramer (52). For this purpose, a glycosyl phosphate donor (48) was first glycosidated with a fluorous linker (49) in the presence of TMSOTf [137].…”

“…The tetrasaccharide was then cleaved from the fluorous support by the treatment with second-generation Grubbs' catalyst to provide a tetrasaccharide (52). The reaction times for glycosylations were 20 seconds for the formation of the disaccharide, and 60 seconds each for the tri-and tetrasaccharides.…”

In Situ Preactivation Strategies for the Expeditious Synthesis of Oligosaccharides: A Review

“…Nicolaou, 51 Danishefsky, 42,52,53 van der Marel, 54 Gin 55 have all contributed significantly to the study of preactivation glycosylations in general, notably, Crich, 56,57 Bols, 58 Whitfield, 49 Boons, 59 and Demchenko 60 have all exploited this minor modification of two-step activation to study such reactive intermediates.…”

Organocatalyzed Glycosylation Reactions of Carbohydrates

“…• glycosylation of an acceptor (R-OH) and • final deprotection step (Scheme 4.1; For current and comprehensive overviews in this field, see: [5][6][7][8][9][10][11][12]). …”