Satoshi Umeda

Synthesis of (1→6)-2,5-anhydro-D-glucitol through cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol and optical resolution ability of its derivative in HPLC

The cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol (1) was carried out using BF3·OEt2 and t-BuOK. The polymer obtained by the polymerization with BF3·OEt2 mainly consisted of (1→6)-bonded 3,4-di-O-allyl-2,5-anhydro-D-glucitol as the five-membered constitutional repeating unit, though it contained a small amount of other cyclic repeating units. On the other hand, during the polymerization using t-BuOK, the stereoregular polymer (1→6)-linked 3,4-di-O-allyl-2,5-anhydro-D-glucitol (2) was synthesized via a regio- and stereoselective mechanism. Cleavage of the allyl ether linkage in polymer 2 occurred to produce the polymer consisting of only 2,5-anhydro-D-glucitol units, i.e., (1→6)-2,5-anhydro-D-glucitol (3). Chromatographic enantioseparation of chloroquine and troger base has been performed on (3,5-dimethylphenyl)carbamate and 4-methylbenzoate derivatives of 3 as a chiral stationary phase for high-performance liquid chromatography.

Synthesis and Cation-Binding Properties of (1→6)-2,5-Anhydro-D-glucitol with 3,4-Di-O-Pentyl and Decyl Groups by Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols

Abstract The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF3OEt2 and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF3O-decyl2 comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl3, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity i...

Synthesis of Poly[(1→6)-2,5-Anhydro-D-Glucitol] by Cationic Cyclopolymerization of 3,4-Di-O-Allyl-1,2:5,6-Dianhydro-D-Mannitol

Abstract The cyclopolymerization of 3,4-di-O-allyl-1,2:5,6-dianhydro-D-mannitol (1d) using BF3·OEt2 produced poly[(1→6)-3,4-di-O-allyl-2,5-anhydro-D-glucitol] (2d). For the polymerization in CH2Cl2 at -10°C, the maximum yield and Mn were obtained as 58.9% and 4890, respectively. The specific rotations ([α]22546) of the obtained polymers were +34.0° ∼ +38.8° (c=1.0 in CHCl3). The deallylation of polymer 2d in acetic acid/ethanol/water using the Pd-C catalyst perfectly proceeded to form poly[(1→6)-2,5-anhydro-D-glucitol] (3). The specific rotations ([α]22546) of the resulting polymers were +17.1° ∼ +18.9° (c=1.0 in H2O). Polymer 2d was soluble in chloroform and tetrahydrofuran, but insoluble in water, whereas polymer 3 was soluble in water but insoluble in chloroform and tetrahydrofuran.

Lymphocyte activation effect of (1→6)-2, 5-anhydro-d-glucitol and it derivatives with 3,4-di-O-methyl and sulfate groups

(1-->6)-2,5-Anhydro-3,4-di-O-methyl-D-glucitol (2a) and (1-->6)-2,5-anhydro-D-glucitol (2c) and its sulfated derivative (2d) were synthesized and their biological activities were evaluated in regards to the effects on murine lymphocytes. The polymers showed different effects on the lymphocytes depending on the substituent groups. The sulfated polymer (2d) induced mitogenic activities, and specifically activated the CD4(-)CD8(-) subset of lymphocytes.