]A potentially versatile synthesis of glycosides

S‐Thiazolinyl (STaz) Glycosides as Versatile Building Blocks for Convergent Selective, Chemoselective, and Orthogonal Oligosaccharide Synthesis

“…[35] The competitive hydrolytic stability studies have been carried out under a range of reaction conditions involving soft thiophilic reagents (N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS)/TfOH), [36,37] relatively hard acidic reagents (TFA or . [38] The formation of the hemiacetal 42 [39] was monitored and quantitatively estimated by TLC.…”

General Aspects of the Glycosidic Bond Formation

“…During the 1970s to early 1980s, a few new classes of glycosyl donors were developed. The following compounds are only the most representative examples of the first wave of the leaving-group development: thioglycosides by Ferrier et al [17], Nicolaou et al [18], Garegg et al [19] and others [20]; cyanoethylidene and orthoester derivatives by Kochetkov and coworkers [21,22]; O-imidates by Sinay and coworkers [23] and Schmidt and Michel [24]; thioimidates including S-benzothiazolyl derivatives by Mukaiyama et al [25]; thiopyridyl derivatives by Hanessian et al [26] and Woodward et al [27] and glycosyl fluorides by Mukaiyama et al [28] (Figure 1.2). Many glycosyl donors introduced during that period gave rise to excellent complimentary glycosylation methodologies.…”

Bromodimethylsulfonium Bromide‐Silver Triflate: A New Powerful Promoter System for the Activation of Thioglycosides

“…[3] The sulfur atom in a thioglycoside is a soft nucleophile, and is therefore able to react selectively with soft electrophiles. [4] In the past years, many types of thiophilic promoters for the activation of thioglycosides have been developed, such as heavy metal cations [e.g., mercury(II) sulfate [5] ], alkylating reagents [e.g., methyl trifluoromethanesulfonate (MeOTf) [6] ], organosulfur compounds [e.g., dimethyl(thiomethyl)sulfonium trifluoromethanesulfonate (DMTST), [7] methylsulfenyl triflate (MeSOTf), [8] phenylsulfenyl triflate (PhSOTf), [9] diphenyl sulfoxide-triflic anhydride (Ph 2 SO/Tf 2 O), [10] benzenesulfinylpiperidine-triflic anhydride (BSP/Tf 2 O), [11] N-(phenylthio)-e-caprolactamtriflic anhydride, [12] benzenesulfinylmorpholine-triflic anhydride (BSM/Tf 2 O), [13] dimethyl disulfide-triflic anhydride (Me 2 S 2 /Tf 2 O) [14] ], organoselenium compounds [e.g., benzeneselenyl triflate (PhSeOTf)], [15] and halogens [e.g., N-iodosuccinimide-triflic acid (NIS/TfOH), [16] N-bromosuccinimide (NBS), [17] iodonium dicollidine perchlorate (IDCP), [18] Ipy 2 BF 4 [19] ]. Although these promoters are convenient for the assembly of oligosaccharides, some drawbacks and limitations have been encountered during glycosylation processes including accessibility, [13] stability, solubility, by-products, [11] purification, [20] and reagent handling issues.…”