Kanai K, Nishigaki J, Taki T, Ogawa S, Suami T
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Japan.
Carbohydr Res. 1987 Dec 1;170(1):47-55. doi: 10.1016/0008-6215(87)85004-8.
1,10-Di-0-acetyl-2,3,4,6,7,8,9-heptadeoxy-2,6-bis(2, 4-dinitrophenylamino)-L-lyxo-decopyranose (7) and -D-ribo-decopyranose (8) have been prepared from methyl 2-acetamido-2,3,4,6-tetradeoxy-6-nitro-alpha-D-erythro-hexopyranoside via a nitro aldol reaction with 4-[(tetrahydropyranyl)oxy]butanal in the presence of cesium fluoride, and their configurations at C-6 have been established by conversion of the precursor of 8, namely, methyl 2,6-diacetamido-10-O-acetyl-2,3,4,6,7,8,9-heptadeoxy-alpha-D - ribo-decopyranoside, into the known methyl 2,6-diacetamido-2,3,4,6,7,8,9,10-octadeoxy-alpha-D-ribo-d ecopyranoside. The title fortimicin A derivatives, 7'-(3-hydroxypropyl)fortimicin A and 6'-epifortimicin A, have been synthesized by condensation of compound 7 and 8, respectively, with 2,5-di-O-benzoyl-1,4-bis[N-(methoxycarbonyl)]fortamine B, followed by deprotection and introduction of a glycyl group. Their antimicrobial activities have been found to be weak compared to that of fortimicin A.
1,10-二-O-乙酰基-2,3,4,6,7,8,9-七脱氧-2,6-双(2,4-二硝基苯基氨基)-L-来苏-脱氧吡喃糖(7)和-D-核糖-脱氧吡喃糖(8)由2-乙酰氨基-2,3,4,6-四脱氧-6-硝基-α-D-赤藓-己吡喃糖苷甲基酯在氟化铯存在下与4-[(四氢吡喃基)氧基]丁醛通过硝基醛醇反应制备，并且通过将8的前体，即2,6-二乙酰氨基-10-O-乙酰基-2,3,4,6,7,8,9-七脱氧-α-D-核糖-脱氧吡喃糖苷甲基酯转化为已知的2,6-二乙酰氨基-2,3,4,6,7,8,9,10-八脱氧-α-D-核糖-脱氧吡喃糖苷甲基酯，确定了它们在C-6处的构型。标题中的福提霉素A衍生物，7'-(3-羟丙基)福提霉素A和6'-表福提霉素A，分别通过化合物7和8与2,5-二-O-苯甲酰基-1,4-双[N-(甲氧基羰基)]福他明B缩合，然后脱保护并引入甘氨酰基合成。已发现它们的抗菌活性与福提霉素A相比较弱。
