Preparation of Hexakis(6-O-mesitylsulfonyl)cyclomaltooctaoses and Structural Validation of the Four Isomers Using Heteronuclear Multiple Bond Correlation Spectroscopy

Abstract

Four cyclomaltooctaose derivatives 1a–d, which possess six mesitylsulfonyloxy groups on their C(6) atoms, were prepared. The assignment of the regiosiomers was performed by observing the long-range coupling through a glycoside linkage between H(1′) –C(4) and C(1′) –H(4) using a heteronuclear multiple-bond correlation (HMBC) method.

Polysulfonylated cyclodextrins. Part 14. Structural validation of tris-and pentakis(6-O-mesitylsulfony)cyclomaltooctaose isomers by1H-NMR spectrometry

“…MeCN (1.0 L) to 40% aq. MeCN (1.0 L) gave trisulfonates as 5a (20.8 mg, 2.0%), 5b (18.7 mg, 1.8%), 5c (15.2 mg, 1.5%), and 5d (15.8 mg, 1.5% 3,4,5,6),4.69,4.79,4.83,4.90,4.94 (8H,ArH). 2f: Rf 0.48; [eluent, 1-propanol:ethyl acetate:water (7:7:5) 3.…”

“…MeCN as an eluent, giving 3a (54.5 mg, 4.7%), 3b (52.4 mg, 4.5%), 3c (31.6 mg, 2.7%), 3d,e (78.5 mg, 6.7%), and 3f,g (120 mg, 10.3%). Further HPLC separation gave the fraction rich in each of 3d-f. 3a: Rf 0.25 [eluent, 1-propanol:ethyl acetate:water (7:7:2)]; tR 43.4 min [gradient, 55%-61% MeCN in water (72 min 3,4,5,6),4.55,4.62,4.69,4.71,4.75,6.98,6.99,7.05,7.06 (10H,ArH). 3b: Rf 0.25 [eluent, 1-propanol: ethyl acetate:water (7:7:2)]; tR 46.5 min [gradient, 55%-61% MeCN in water (72 min); flow rate, 1.0 ml/min]; 1 H-NMR (Me 2 SO-d6-D 2 O): δ 2.…”

“…3b: Rf 0.25 [eluent, 1-propanol: ethyl acetate:water (7:7:2)]; tR 46.5 min [gradient, 55%-61% MeCN in water (72 min); flow rate, 1.0 ml/min]; 1 H-NMR (Me 2 SO-d6-D 2 O): δ 2. 2.37,2.39,2.44,2.48 (CH 3 ),3,4,5,6),4.57,4.64,4.67,4.71,4.77,4.82,4.89 (8H,6.94,6.96,7.02,7.03,7.04 (10H,ArH). 3c: Rf 0.25 [eluent, 1-propanol:ethyl acetate:water (7:7:2)]; tR 51.4 min [gradient, 55%-61% MeCN in water (72 min 3,4,5,6),4.64,4.70,4.78,4.87,4.89 (8H,6.98,7.00,7.02,7.03,7.04 (10H,ArH).…”

“…2.37,2.39,2.44,2.48 (CH 3 ),3,4,5,6),4.57,4.64,4.67,4.71,4.77,4.82,4.89 (8H,6.94,6.96,7.02,7.03,7.04 (10H,ArH). 3c: Rf 0.25 [eluent, 1-propanol:ethyl acetate:water (7:7:2)]; tR 51.4 min [gradient, 55%-61% MeCN in water (72 min 3,4,5,6),4.64,4.70,4.78,4.87,4.89 (8H,6.98,7.00,7.02,7.03,7.04 (10H,ArH). 3d: Rf 0.25 [eluent, 1-propanol:ethyl acetate:water (7:7:2)]; tR 55.0 min [gradient, 55%-61% MeCN in water (72 min); flow rate, 1.0 ml/min]; 1 H-NMR (Me 2 SO-d6-D 2 O): δ 3.…”

Chemical Modification of Cyclodextrin and Amylose by Click Reaction and Its Application to the Synthesis of Poly-alkylamine-Modified Antibacterial Sugars

“…To this end, poly-sulfonylated CD derivatives have been studied. [2][3][4] The second important thing to be examined is a method for introducing functional moieties onto a CD molecule. Recently we found that CD derivatives 1 possessing polyamino groups (more than six on the molecule) strongly disrupted bacterial membranes; the addition of benzyl moieties to the amino groups (CD derivative 2) enhanced the membrane permeabilization and inhibited bacteria proliferation 5) (Chart 1).…”