Synthesis of Glyco‐Silicas by Cu(I)‐Catalyzed “Click‐Chemistry” and their Applications in Affinity Chromatography

Abstract

The covalent immobilization of suitable alkyne/azide carbohydrate derivatives on complementarily functionalizated azide/alkyne silica was performed by click ligation througth the Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction of such compounds. The new glyco-silicas have shown to be efficient and valuable bio-selective affinity chromatographic supports for the purification of lectins as well as for the one-pot fluorescent labeling of those proteins. The synthetic methodology is simple, high yielding and flexible, allowing the preparation of tailored glyco-silicas with potential future applications in the inmobilization of other biomolecules.

Non‐Magnetic and Magnetic Supported Copper(I) Chelating Adsorbents as Efficient Heterogeneous Catalysts and Copper Scavengers for Click Chemistry

“…Secondly, bearing in mind that Cu-catalyzed triazole formations are in many cases accomplished using an excess of one of the clickable reagents, particularly, a surplus of the azido building block to avoid C À C coupling reactions of two alkyne moieties, and also the plausible implementation of the Si-Lm adsorbents in click reactions under continuous flow conditions, [24] the dialkynyl derivative 18 and the monoazide derivative of b-cyclodextrin 25 were reacted with an excess of the complementary a-Man azide (23) and the b-Glc alkynyl (15) derivatives, respectively, using CuCl as catalyst (Table 6, entries 4 and 5). The extra amounts of the unreacted clickable reagents were first removed by using alkyne or azido functionalized silicas [33] as "click chemistry scavengers" followed by subsequent treatment with Si-BPA to eliminate copper species. The use of comparable polystyrene-based functionalized alkyne and azide resins as azide and alkyne scavengers has been previously reported in the literature.…”

A multivalent inhibitor of the DC-SIGN dependent uptake of HIV-1 and Dengue virus

“…Dichloromethane, methanol, N,N-diisopropylethylamine and triethylamine were dried over calcium hydride; THF was distilled over sodium, N,N-dimethylacetamide (DMA) was dried over activated molecular sieves (4 Å [29] have been previously described. The tetravalent mannosylated dendrimer 11.5 is a known compound.…”

“…The basic structures 7, 9, 11, 13 can lead to di-, tri-, tetra-and hexa-valent presentations of a monovalent ligand, respectively. Additionally, the known trivalent dendron 14 [29] was prepared from 10 (Scheme 1). Dendron 14 can be functionalized by Cu(I) catalyzed azidealkyne cycloaddition (CuAAC) with three copies of a ligand and, after transformation of the chloride tethered to the focal point into an azide (yielding 15, Figure 2), it can be clicked on other polyalkynes such as 7, 9, 11, 13, leading to compounds with higher valency and different shapes were built using mannose 5, the pseudo-dimannoside 3 and the pseudo-trimannoside 2 as the monovalent ligand (see Supplementary Information).…”

A bioinspired heterogeneous catalyst based on the model of the manganese-dependent dioxygenase for selective oxidation using dioxygen

“…Synthesis of 3-azidopropyltriethoxysilane. 31 Sodium azide (27 g, 0.41 mol) was added portionwise to a solution of 3-chloropropyltriethoxysilane (20 g, 83 mmol) and tetrabutylammonium iodide (153 mg, 0.42 mmol) in 220 mL of butanone. The mixture was then stirred at reux for 5 d under nitrogen.…”