Common side reactions of the glycosyl donor in chemical glycosylation. (18th May 2015)

• Record Type: Journal Article
• Authors: Christensen, Helle M.; Oscarson, Stefan; Jensen, Henrik H.
• Is Part Of: Carbohydrate research. Volume 408(2015)
• Page Start: 51
• Page End: 95
• Publication Date: 2015-05-18
• Subjects: By-products -- Hydrolysis -- Elimination -- Thioglycosides -- Trichloroacetimidates; 5AcNeu 5-acetylneuraminic acid -- Boc tert-butoxycarbonyl -- Cbz benzyloxycarbonyl -- Cp cyclopentadienyl -- DIPEA diisopropylethyl amine -- ClBn 4-chlorobenzyl -- DMDO dimethyldioxirane -- DMP 2, 6-dimethylphenyl -- DTBMP 2, 6-di-tert-butyl-4-methylpyridine -- Fmoc 9-fluorenylmethoxycarbonyl -- LG leaving group -- MP 4-methoxyphenyl -- MS molecular sieves -- MSB methyl sulfenyl bromide -- NAP 2-naphthylmethyl -- NIS N-iodosuccinimide -- NMM N-methylmorpholine -- Tol ortho-tolyl -- PG protecting group -- PMB para-methoxybenzyl -- ROMP ring opening metathesis polymerisation -- TBAB tetrabutylammonium bromide -- TBAI tetrabutylammonium iodide -- TBDPS tert-butyldimethylsilyl -- TBPA+ tris(4-bromophenyl)ammonium hexachloroantimonate -- TBS tert-butyldimethylsilyl -- TCA trichloroacetyl -- Tf triflyl -- TFA trifluoroacetyl -- TIPS triisopropylsilyl -- TMS trimethylsilyl -- TMSE 2-(trimethyl-silyl)ethyl -- TMU tetramethylurea -- Troc trichloroethoxycarbonyl; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2015.02.007
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: Chemical glycosylation is central to carbohydrate chemistry and is generally recognised as a challenging reaction. This review describes the most reoccurring side reactions of glycosyl donors in glycosylation and how scientists have attempted to explain their observations and in some cases succeeded in solving a particular encountered problem. The topics covered are donor hydrolysis, elimination to form glycals, intermolecular aglycon transfer of thioglycosides and glycosyl imidate rearrangement. Graphical abstract: Highlights: Glycosyl donor hydrolysis is discussed. Glycosyl donors may undergo elimination reactions in competition with substitution. The sulfur atom of thioglycosides may act as a nucleophile in glycosylation. Glycosyl trichloroacetimidates can undergo rearrangement to amides.