Regio- and Stereoselectivity in Cationic Cyclopolymerizations of 1,2:5,6-Dianhydro-3,4-di-O-methyl-D-mannitol and -L-iditol and the Synthesis of Poly[(1.fwdarw.6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol]

Kakuchi, Toyoji; Satoh, Toshifumi; Umeda, Satoshi; Hashimoto, Hisaho; Yokota, Kazuaki

doi:10.1021/ma00120a033

Cited by 27 publications

(40 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6)-2,5-anhydro-D-glucitol (16). [59] The remaining signals were similar to those of 2,5-anhydro-3,4,6-tri-O-methyl-D-glucitol (17), [57] 2,5-anhydro-3,4-di-O-methyl-D-glucitol (18), [61] 2,5 -anhydro -1,3,4,6-tetra-O-methyl -D-glucitol (19), [57] 2,5-anhydro-1,6-di-O-methyl-D-glucitol (20), [59] and (1 ! 6)-bonded 3,4-O-methyl-2,5-anhydro-D-glucitol (21), [57] which were the model compounds for linear units, semi-dendritic units, and dendritic units of 2,5-anhydro-D-glucitol ( Figure 2).…”

Section: Synthesis Of Hyperbranchedmentioning

confidence: 78%

Synthesis of Hyperbranched Carbohydrate Polymers by Ring‐Opening Multibranching Polymerization of Anhydro Sugar

Satoh

Kakuchi

2007

Macromolecular Bioscience

Self Cite

View full text Add to dashboard Cite

The synthesis of novel hyperbranched carbohydrate polymers, prepared by the ring-opening multibranching polymerizations of anhydro and dianhydro sugars, is described. The hyperbranched carbohydrate polymers were formed by the cationic polymerization of 1,6-anhydro-beta-D-hexopyranose, 1,4-anhydrotetritol, 2,3-anhydrotetritol, and 1,2:5,6-dianhydro-D-mannitol. These polymerizations proceeded without gelation to produce water-soluble hyperbranched carbohydrate polymers with controlled molecular weights and narrow polydispersities. The values for the degree of branching of the polymers were in the range of 0.28-0.50. The polymerization method, which proceeds through a ring-opening reaction by a proton-transfer reaction mechanism, is a facile method leading to a spherical carbohydrate polymer with a high degree of branching.

show abstract

Section: Synthesis Of Hyperbranchedmentioning

confidence: 78%

Synthesis of Hyperbranched Carbohydrate Polymers by Ring‐Opening Multibranching Polymerization of Anhydro Sugar

Satoh

Kakuchi

2007

Macromolecular Bioscience

Self Cite

View full text Add to dashboard Cite

show abstract

“…2,5-Anhydro-1 ,3,4,6-tetra-0-methyl-o-glucitol (8) was synthesized from 1 by the same procedure in a previous report. 15 (4) Monomer 4 was prepared from o-glucitol according to the reported procedure. 20 …”

Section: Methodsmentioning

confidence: 99%

“…15 In order to confirm the cyclic structural unit in polymer 5, the 13 C NMR spectra of the polymers were compared with those of three 2,5-anhydrohexitols, i.e., 2,5-anhydro-1 ,3,4,6-tetra-0-methyl-o-mannitol (6), -L-iditol (7), and -o-glucitol (8). Table III summarizes the 13 C NMR chemical shifts of these compounds.…”

Section: Polymer Structurementioning

confidence: 99%

“…1 -11 The cyclopolymerization of 1,2: 5,6-dianhydrohexitol is also a useful methodY -19 Both 1,2: 5,6-dianhydro-3,4-di-0-methylo-mannitol (1) and -L-iditol (2) were cyclopolymerized using boron trifluoride etherate (BF 3 · 0Et 2 ) to produce a polymer consisting mainly of 2,5-anhydro-3,4-di-0-methyl-o-glucitol as the constitutional cyclic unit. 15 The anionic cyclopolymerization of 1 using potassium tert-butoxide (t-BuOK) was highly regio-and stereoselective and the polymer obtained had a stereospecific structure, i.e., (1->6)-2,5-anhydro-3,4-di-0-methyl-oglucitol (3). 16 • 17 o-Mannitol and L-iditol have C 2 symmetry, and the two epoxy groups in the monomer are equal in reactivity.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Satoh

Hatakeyama

Umeda

et al. 1996

Polym J

Self Cite

View full text Add to dashboard Cite

“…Previously, we reported the difference in the cyclopolymerization tendency between 3,4-di-0-methyl and 3,4-0-isopropylidene-1 ,2: 5,6-dianhydro-o-mannitols, i.e., the former polymerization produced regio-and stereospecific polymer 1, 7 whereas the latter yielded polymer 2 consisting of cyclic and acyclic constitutional repeating units. 8 Thus they are suitable polymers for investigating the effect of polymer structure on the molecular recognition toward a cationic guest.…”

mentioning

confidence: 97%

Macromolecular Ionophore II. Metal Cation-Binding Property of (1→6)-2,5-Anhydro-D-glucitol

Kakuchi

Hatakeyama

Kanai

et al. 1999

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The cation-binding property has been studied for polymer 1 consisting of 3,4-di-0-methyl-D-glucitol units, ( 1-->6)-2,5-anhydro-3,4-di-0-methyl-D-glucitol, and polymer 2 with a mole fraction of cyclized units of 0.52 synthesized by the polymerization of 1 ,2:5,6-dianhydro-3,4-0-isopropylidene-D-mannitol. Polymer 1 exhibited cation-binding selectivity in the order of K + > Rb + > Cs + > Na + > Li +,which was estimated using both liquid-liquid extraction and liquid-membrane transport methods. On the other hand, 2 showed an extremely low cation-binding characteristic in both extraction yield and selectivity, and the yield of K + for 2 was ca. one-eighth of that for 1. There was a need for ca. 21-25 and ca. 200--400 repeating units in the complexes of 1 and 2 with K +, respectively. The binding ability of 1 strongly depended on the radius of the metal cations, and the extraction yields were relatively low for a cation with a radius of 1.12A and below (Mg 2 +, Li+, Ni2+, Co2+, Cu 2 +, Zn 2 +, Cd2+, Na +, Ca 2 +, and Sr 2 +) and high for a cation with a radius of 1.20 A and above (Pb2+, Ag+, K +, Ba2+, Rb+, and Cs+).KEY WORDSMacromolecular ionophores such as poly(cyclooxalkane)diyl, 1 poly(7-oxanorbornene), 2 and (1---+6)-2,5-anhydro-3,4-di-0-alkyl-o-glucitol (alkyl= CH 3 , 1) 3 -6 recognize a metal cation and form a complex with it, as do naturally occurring acyclic ionophores. In the hostguest complexations, the molecular recognitions are supposed to realize that helical conformers of these polymers vary their pitch and cavity size for optimizing multidentate coordination with a given cation. Therefore, it is of interest to elucidate the effect of the structural regularity and number of repeating units in the host polymer on the molecular discrimination, when the polymer forms the complex with a cationic guest.Previously, we reported the difference in the cyclopolymerization tendency between 3,4-di-0-methyl and 3,4-0-isopropylidene-1 ,2: 5,6-dianhydro-o-mannitols, i.e., the former polymerization produced regio-and stereospecific polymer 1, 7 whereas the latter yielded polymer 2 consisting of cyclic and acyclic constitutional repeating units. 8 Thus they are suitable polymers for investigating the effect of polymer structure on the molecular recognition toward a cationic guest. Moreover, the molecular recognition property of a macromolecular ionophore is of great interest in relation to the fact that a naturally occurring acyclic ionophore transports a metal cation through a liquid membrane system. In this paper, we report that the alkali metal cationbinding properties of I and 2 are characterized using a liquid-liquid extraction method and those for I using a liquid-membrane transport system. For the complexes with K +, the number of repeating units in I and 2 is estimated by changing the ratio of the units to K +. In addition, the relation between the metal cation radius and the binding property of 1 is clarified using various metal cations. EXPERIMENTAL MaterialsThe synthesis of polymers I and 2 was repor...

show abstract

Regio- and Stereoselectivity in Cationic Cyclopolymerizations of 1,2:5,6-Dianhydro-3,4-di-O-methyl-D-mannitol and -L-iditol and the Synthesis of Poly[(1.fwdarw.6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol]

Cited by 27 publications

References 6 publications

Synthesis of Hyperbranched Carbohydrate Polymers by Ring‐Opening Multibranching Polymerization of Anhydro Sugar

Synthesis of Hyperbranched Carbohydrate Polymers by Ring‐Opening Multibranching Polymerization of Anhydro Sugar

Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Macromolecular Ionophore II. Metal Cation-Binding Property of (1→6)-2,5-Anhydro-D-glucitol

Contact Info

Product

Resources

About