Synthesis of neoglycoconjugates by the desulfurative rearrangement of allylic disulfides.
Two series of neoglycosyl donors are prepared on the basis of connection of an allylic disulfide motif to the anomeric center via a simple O-glycosyl linkage or N-glycosyl amide unit. Conjugation of both sets of donors to cysteine in peptides is demonstrated through classical disulfide exchange followed by the phosphine-mediated desulfurative allylic rearrangement resulting in neoglycopeptides characterized by a simple thioether spacer. The conjugation reaction functions in the absence of protecting groups on both the neoglycosyl donor and peptide in aqueous media at room temperature.
Crich
David
D
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA. dcrich@chem.wayne.edu
Yang
Fan
F
D000498:Allyl Compounds; D003545:Cysteine / Q000737:chemistry; D004220:Disulfides / Q000737:chemistry*; D006001:Glycoconjugates / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D008968:Molecular Conformation; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry; D010455:Peptides / Q000737:chemistry
D000498:Allyl Compounds; D004220:Disulfides; D006001:Glycoconjugates; D009943:Organophosphorus Compounds; D010455:Peptides; C061896:triphenylphosphine; C028009:diallyl disulfide; D003545:Cysteine