Premium
Chiral Polymers Containing a Carbohydrate Moiety: Synthesis
Author(s) -
MaślińskaSolich Jolanta,
Kukowka Sylwia
Publication year - 2004
Publication title -
macromolecular bioscience
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.924
H-Index - 105
eISSN - 1616-5195
pISSN - 1616-5187
DOI - 10.1002/mabi.200300049
Subject(s) - chemistry , diastereomer , acetal , moiety , condensation polymer , polymer chemistry , polymer , catalysis , comonomer , macromolecule , nuclear magnetic resonance spectroscopy , copolymer , organic chemistry , biochemistry
Summary: This paper reports the preparation of poly(acetal‐ethers) by two alternative synthetic pathways (alkaline and acid‐catalyzed conditions). Polycondensations of methyl 2,3:4,6‐di‐ O ‐salicylidene‐ α ‐ D ‐mannopyranoside ( 3 ) (mixtures of endo‐H and exo‐H dioxolan‐2‐yl‐diastereomers) with 1,4‐dibromobutane ( 4 ) (method I a and I b) were performed in solvents (DMF, butyl acetate/DMF, DMSO) and were catalyzed by K 2 CO 3 /KI or KOH. A similar polymer ( 6 ) was formed by the reaction of methyl α ‐ D ‐mannopyranoside ( 1 ) and 1,4‐bis(2‐formylphenoxy)butane ( 7 ), catalyzed by p ‐toluenesulfonic acid (method II). Regardless of conversion or initial comonomer feed ratios, the composition of the polycondensates depended on the reaction conditions, leading to the formation of macrocyclic [1 + 1] ( 5 ) and [2 + 2] compounds, which were macromolecules with diverse molecular weights and optical properties. The regioselective polycondensation was examined by 1 H NMR spectroscopy of selected polymers. In the case of 5‐membered cyclic acetal units, mixtures of the endo‐H and exo‐H dioxolan‐2‐yl system, diastereomers were formed in the polymer chain. The macrocycles and linear oligomers were identified by NMR and electrospray mass spectrometry (ESI‐MS). Thermodynamically controlled reactions for making macrocycles as well as oligomers in the absence of templates are also discussed.