Glycal assembly by the in situ generation of glycosyl dithiocarbamates.
Glycal assembly offers an expedient entry into β-linked oligosaccharides, but epoxyglycal donors can be capricious in their reactivities. Treatment with Et(2)NH and CS(2) enables their in situ conversion into glycosyl dithiocarbamates, which can be activated by copper triflate for coupling with complex or sterically congested acceptors. The coupling efficiency can be further enhanced by in situ benzoylation, as illustrated in an 11-step synthesis of a branched hexasaccharide from glucals in 28% isolated yield and just four chromatographic purifications.
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, USA.
Panuwat
P
Padungros
Laura
L
Alberch
Alexander
A
Wei
D002236:Carbohydrate Conformation; D006027:Glycosides / Q000737:chemistry*; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D013859:Thiocarbamates / Q000737:chemistry*
D006027:Glycosides; D009844:Oligosaccharides; D013859:Thiocarbamates