Ashwell M, Jones A S, Walker R T
Nucleic Acids Res. 1987 Mar 11;15(5):2157-66. doi: 10.1093/nar/15.5.2157.
1-(2,3-Epoxy-5-O-trityl-beta-D-lyxofuranosyl)uracil was treated with a number of carbon nucleophiles. Ethynyl lithium gave 3'-deoxy-3'-ethynyl-5'-O-trityl-ara-uridine, which was reduced to the corresponding 3'-ethenyl compound. Sodium cyanide gave 3'-cyano-3'-deoxy-5'-O-trityl-ara-uridine which upon alkaline hydrolysis gave the corresponding 3'-carboxamido compound. 1,3-Dithian-2-yl lithium gave 3'-deoxy-3'-(1,3-dithian-2-yl)-5'-O-trityl-ara-uridine. The trityl group was removed from each of these compounds by mild acidic hydrolysis. Treatment of 2 with 0.1M H2sO4 and mercury (II) acetate afforded 3'-acetyl-3'-deoxy-ara-uridine which upon reduction with NaBH4 gave 3'-deoxy-3'-(1-hydroxyethan-1-yl)-ara-uridine. Acetylation of 6 yielded 5'-O-acetyl-3'-acetyl-2',3'-didehydro-2',3'-dideoxyuridine which upon reduction with NaBH4 produced a mixture of 5'-O-acetyl-2',3'-didehydro-2',3'-dideoxy-3'-(1-hydroxyethan -1-yl)uridine and 1-(R)[5-(S)-acetoxymethyl-4-(1-hydroxyethan-1-yl)-tetrahydrofuran- 2-yl]- uracil. Reduction of 14 with Raney nickel followed by removal of the trityl group gave 3'-deoxy-3'-methyl-ara-uridine.
1-(2,3-环氧-5-O-三苯甲基-β-D-来苏呋喃糖基)尿嘧啶与多种碳亲核试剂反应。乙炔基锂生成3'-脱氧-3'-乙炔基-5'-O-三苯甲基阿糖尿苷，后者被还原为相应的3'-乙烯基化合物。氰化钠生成3'-氰基-3'-脱氧-5'-O-三苯甲基阿糖尿苷，其经碱性水解后得到相应的3'-羧酰胺化合物。1,3-二硫杂环戊烷-2-基锂生成3'-脱氧-3'-(1,3-二硫杂环戊烷-2-基)-5'-O-三苯甲基阿糖尿苷。通过温和的酸性水解从这些化合物中除去三苯甲基。用0.1M硫酸和醋酸汞(II)处理2得到3'-乙酰基-3'-脱氧阿糖尿苷，其用硼氢化钠还原后得到3'-脱氧-3'-(1-羟乙基)-阿糖尿苷。6的乙酰化产物为5'-O-乙酰基-3'-乙酰基-2',3'-二脱氢-2',3'-二脱氧尿苷，其用硼氢化钠还原后得到5'-O-乙酰基-2',3'-二脱氢-2',3'-二脱氧-3'-(1-羟乙基)尿苷和1-(R)[5-(S)-乙酰氧基甲基-4-(1-羟乙基)-四氢呋喃-2-基]尿嘧啶的混合物。用雷尼镍还原14，然后除去三苯甲基得到3'-脱氧-3'-甲基阿糖尿苷。
