Development and Investigation of a Dehydrative Glycosylation With Activated Diphenyl Sulfonium Reagents

104 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2001.Mechanistic studies suggest that the glycosyl donor is initially activated via nucleophilic attack of the hemiacetal hydroxyl upon the sulfonium center of diphenylsulfide bis(trifluoromethanesulfonate), leading to formation of a glycosyl oxosulfonium. Low temperature NMR studies have revealed that a glycosyl pyridiniurn is subsequently formed in the latter stages of the glycosylation. Additional data suggests, however, that the reactive intermediate is likely a glycosyl oxocarbenium.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD