核苷研究——Ⅴ.双乙酰赛吲哚霉素的全合成

Studies on Nucleosides——Ⅴ. Total Synthesis of Diacetyl Neosidomycin

赛吲哚霉素的双乙酰衍生物已由吲哚瞒-吲哚法合成.吲哚-3-乙酸经催化氢化,甲酯化和氨解反应得到吲哚瞒-3-乙酰胺(9);将4-去氧-D-核-吡喃己糖以三苯甲基保护后乙酰化.消除保护基再经氧化和甲酯化等反应,得到1,2,3-O-三乙酰基-4-去氧-β-D-核-吡喃己糖醛酸甲酯(6),将化合物6和9先缩合后脱氢即得到赛吲哚霉素的双乙酰衍生物2.赛吲哚霉素的类似物1-(3-氨羰甲基吲哚基)-2,3,4,6-O-四乙酰基-β-D-吡喃葡萄糖苷(13)也由相似的方法合成.

The diacetate of neosidomycin had been synthesized by indoline - indole method. Firstly, indoline - 3 - acetamide ( 9) was prepared from indole - 3 - acetic acid by catalytic hydrogenation, esterification and aminolysis. And then methyl 1,2,3, - O - triacetyl - 4 - deoxy - β- D - ribo - hexopyranuronate(6) was synthesized from 4 - deoxy - D - ribo - hexopyranose ( 3 ) through triphenylmethylation, acetylation, detriphenylmethylation, oxidation and esterification. The indoline - N - glycoside 10 was obtained by the condensation of 9 and 6. Finally, the diacetate of neosidomycin 2 (methyl [1 - (3 - carbamoylmethylindoyl) - 2, 3 - O -diacetyl - 4 - deoxy - D-ribo - hexopyranoside]uronate), was prepared by the dehydrogenation of 10 with DDQ. With the similar method 1 - (3 - carbamoylmethylindoyl) - 2, 3, 4, 6 - O -tetraacetyl - β - D - glucopyranoside (13) was synthesized.