Sucrose Scaffold Research Articles

Synthesis of an Ethylenediaminetetraacetic Acid-like Ligand Based on Sucrose Scaffold and Complexation and Proton Relaxivity Studies of Its Gadolinium(III) Complex in Solution.

Sucrose constitutes a non-toxic, biodegradable, low-cost and readily available natural product. To expand its utility, we developed total synthesis for a ligand based on a sucrose scaffold for potential use as a metal chelation agent. The designed target (compound 2) has a metal-chelating functionality at both the C-6 and C-6' positions, which can provide a first coordination sphere of eight valencies. The designed total synthesis was highly efficient. To demonstrate the utility of the ligand, we studied its complexation with Gd(III). Using potentiometric titration and high-resolution mass spectrometry, we confirmed the formation of a 1:1 complex with Gd(III), which has a respectable formation constant of ~1013.4. Further NMR relaxivity studies show that the Gd(III) complex has a relaxivity (r1) of 7.6958 mmol-1 s-1.

Synthesis of sulfur containing macrocycles with sucrose scaffold

The first synthesis of sucrose-based macrocycles containing two sulfur atoms in the ring was presented. The synthesis was initiated from known 6,6′-dideoxy-6,6′-di-chloro-1′,2,3,3′,4,4′-hexa-O-benzyl-sucrose in which both terminal positions (C6 and C6′) were elongated by the -S–CH2–CH2-OH unit. The resulting diol was converted into dichloride and reacted further with a series of diamines which afforded the corresponding macrocyclic derivatives in high yields.

First synthesis of cryptands with sucrose scaffold.

Cryptands with sucrose scaffold, an unknown class of such derivatives, were prepared from the readily available 2,3,3’,4,4’-penta-O-benzylsucrose and 1’,2,3,3’,4,4’-hexa-O-benzylsucrose.

Macrocyclic derivatives with a sucrose scaffold: insertion of a long polyhydroxylated linker between the terminal 6,6′-positions

A series of five new macrocyclic hybrids with a sucrose scaffold were prepared by the reaction of activated 1′,2,3,3′,4,4′-hexa-O-methylsucrose with diversely functionalized d-mannitols.

Synthesis of aza-crown analogues and macrocyclic bis-lactams with sucrose scaffold

2,3,3′,4,4′-Penta-O-benzylsucrose was converted into the corresponding diaminoalcohol which was used as a key building block in the synthesis of the analogues of aza-crown ethers and bis-lactams.

Synthesis of novel macrocyclic derivatives with a sucrose scaffold by the RCM approach

1′2,3,3′4,4′-Hexa-O-benzylsucrose was esterified at both terminal positions with an unsaturated acid derived from d-glucose. Cyclization of the resulting di-olefin under the RCM conditions afforded the corresponding 21-membered macrocyclic unsaturated di-ester. The same sequence of reactions performed for 6,6′-diamino-6,6′-dideoxy-1′2,3,3′4,4′-hexa-O-benzylsucrose gave a 21-membered macrocyclic unsaturated di-amide. The cyclization in both cases was highly selective and provided a cyclic olefin with the E-geometry exclusively. Dihydroxylation of the olefin provided only one diol with relative configuration consistent with Kishi's rule. The absolute configuration was determined by CD spectroscopy.

Short Synthesis of Diamide-Linked Sucrose Macrocycles

A convenient route to macrocyclic diamide-linked macrocyclic derivatives with a sucrose scaffold is presented. Reaction of sucrose based amines (o- and m-) with acid dichlorides afforded the monomeric macrocycles in excellent yields, while reaction of the p-amines also provided dimeric products.

New Methodology for the Differentiation of the Primary Hydroxyl Groups in 2,3,3′,4,4′-Penta-O-Benzylsucrose: Convenient Approach to Sucrose Monophosphines

Two new routes to derivatives of 2,3,3′,4,4′-penta-O-benzylsucrose with differently protected primary hydroxyl groups were elaborated. One of these compounds, 2,3,3′,4,4′-penta-O-benzyl-6′-O-mesylsucrose, was used in a model synthesis of the 6′-phosphine with sucrose scaffold. Elimination of the mesyloxy- group under the reaction conditions was also noted providing the 5′,6′-unsaturated sucrose derivative.

Synthesis and cellular uptake properties of guanidine-containing molecular transporters built on the sucrose scaffold

Novel sucrose-based G7 molecular transporters show different patterns of intracellular localization depending on the nature of the linker chains as well as the fluorescent dyes.