RING-OPENING POLYMERIZATION OF MODIFIED 1,4-ANHYDRODEOXYRIBOSE DERIVATIVES AND SYNTHESIS OF 3-DEOXY-(1-]5)-ALPHA-D-RIBOFURANAN

被引:7
作者
ODA, K [1 ]
YOSHIDA, T [1 ]
URYU, T [1 ]
机构
[1] UNIV TOKYO,INST IND SCI,MINATO KU,TOKYO,TOKYO 106,JAPAN
关键词
D O I
10.1021/ma00080a001
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Selective ring-opening polymerization of a 1,4-anhydro-2-O-(tert-butyldimetbylsilyl-3-deoxy-alpha-D-ribopyranose (A3DSR) was carried out by a number of Lewis acid catalysts to give stereoregular 3-deoxyribofuranans. It was found that the polymerization by phosphorus pentafluoride catalyst at -78 degrees C gave a poly(A3DSR) with [alpha](D) = +85 degrees consisting of 1,5-alpha-linked furanosidic units in the polymer backbone, while the polymerization at 0 degrees C gave a poly(A3DSR) with [alpha](D) = -46 degrees which was composed of 1,5-beta-linked furanosidic units. 1,4-Anhydro-3-O-(tert-butyldimethylsilyl)-2-deoxy-alpha-D-ribopyranose (A2DSR) was also polymerized by Lewis acid catalysts to give stereoirregular polymers consisting of mixed structures of alpha- and beta-units. The desilylation of the poly(A3DSR) was carried out by a fluoride ion in THF to give a 3-deoxy-(1-->5)-alpha-D-ribofuranan. The structure analysis of polymers was performed by C-13 NMR spectroscopy, specific rotation, and hydrolysis studies. The effects of catalyst, polymerization temperature, and time on the polymer stereoregularity were examined, and the mechanism of the stereoregular polymerization was discussed.
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页码:315 / 319
页数:5
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