Orthogonal One-Pot Synthesis of Oligosaccharides Based on Glycosyl ortho-Alkynylbenzoates

Abstract

One of the most popular one-pot glycosylation strategies is orthogonal one-pot synthesis, which was mainly based on thioglycosides. Despite its successful application, shortcomings of thioglycosides including aglycon transfers, interference of departing species and unpleasant odor restrict its application scope. Herein, we report a new and efficient orthogonal one-pot synthesis of oligosaccahrides based on glycosyl ortho-alkynylbenzoate, which solves the issues of thioglycoside-based orthogonal one-pot synthesis. Over a dozen of oligosaccharides have been efficiently synthesized by this method.

Glycosyl ortho-(1-phenylvinyl)benzoates versatile glycosyl donors for highly efficient synthesis of both O-glycosides and nucleosides

“…However, the number of leaving groups that could be utilized in multistep orthogonal one-pot synthesis is still limited. Recently, the group of Xiao 38 developed orthogonal one-pot synthesis of oligosaccharides based on glycosyl ABz, which solved the shortcomings including aglycon transfer, high electrophilic character of departing species, and unpleasant odor inherent to thioglycosides based orthogonal onepot glycosylation. We envisioned that orthogonal one-pot synthesis of oligosaccharides based on glycosyl PVB could also be explored to streamline chemical synthesis of oligosaccharides in one-pot, whose sulfated derivatives exhibit significant proangiogenic activity 60 .…”

“…For example, methods using readily prepared and stable glycosyl donors, cheap and readily available promoters, and mild reaction conditions are still limited. The number of leaving groups that could be combined to achieve multi-steps one-pot synthesiss of oligosaccharides is still rare 13,14,38,39 . Furthermore, general glycosylation methods suitable for industrial appllications with lower costs for efficient synthesis of both O-glycosides and nucleosides remain extremely rare.…”

Triflic Imide‐Catalyzed Glycosylation of Disarmed Glycosyl ortho‐Isopropenylphenylacetates and ortho‐Isopropenylbenzyl Thioglycosides

“…The data are identical with those in the literature. [40] Methyl Following the procedure for 5 a, donor 3 a (80.8 mg, 107.05 μmol, 1.5 equiv) and alcohol 4 i (70.0 mg, 71.36 μmol, 1.0 equiv) were treated with Tf 2 NH (4.0 mg, 14.23 μmol, 0.2 equiv) at 0 °C to give 5 i (89.0 mg, 57.07 μmol, 80 %) as a white foam after purification by silica gel column chromatography (3 : 1, PE/EA, v/v). a ½ � 27 D = + 66.5 (c 2.0, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.94-7.82 (m, 12H), 7.76 (dd, J = 7.7, 4.4 Hz, 4H), 7.67 (dd, J = 7.8, 3.9 Hz, 4H), 7.48-7.38 (m, 6H), 7.…”

Modular Synthesis of Nona‐Decasaccharide Motif from Psidium guajava Polysaccharides: Orthogonal One‐Pot Glycosylation Strategy

“…It is noteworthy that the orthogonal one-pot glycosylation strategy using the glycosyl ABz for the synthesis of 1 and shorter sequences (2-4)precludes aglycon transfers,the interference of departing species,a nd unpleasant odors inherent to thioglycoside-based orthogonal one-pot synthesis. [23] The 1 HNMR spectra, in particular the chemical shifts of the anomeric protons of 1 and the shorter sequences 2-4 are highlighted in Figure 2. Assignment of the NMR signals of 1-4 as well as their MALDI-TOF mass spectra confirmed the structures (see the Supporting Information for details).…”