The Development of a Generally Synthetic Method of D-and L-Deoxyfuranose

D-和L-脱氧呋喃糖通用合成方法的开发

• 批准号: 07454198
• 负责人: SATO Tsuneo
• 金额: $ 1.79万
• 依托单位: Kurashiki University of Science and the Arts
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454198/
• 关键词: D-2,3-dideoxyribose; L-2,3-dideoxyribose; D-2-deoxyribose; D-3-deoxyribose; D-deoxysugar; L-deoxysugar; deoxy sugar having branched chain; 2-デオキシ糖; 分枝糖; デオキシ糖; 3-メチルリボフラノース; 4-メチルリボフラノース; 2,3-ジデオキシ糖; アリル陰イオン; 位置選択性; ミズロウ-エバンス転位; 不斉エポキシ化

1.The reaction of the allyl anion derived from 1-methoxy-3-(phenylthio)-1-propene with benzyl(R)-glycidyl ether was provided(E,S)-6-benzyloxy-5-hydroxy-2-hexenal, which was then transformed into(E,S)-6-benzyloxy-5-tert-butyldimethylsiloxy-2-hexen-1-ol in two steps : (a)tert-BuMe_2SiCl ; (b)NaBH_4 Sharpless-Katsuki asymmetric epoxidation with D-diethyl tartrate followed by treatment with C_6H_5CH_2OH afforded(2R,3S,5S)-3,6-bis(benzyloxy)-5-tert-butyldimethylsiloxy-1,2-hexanediol. This compound was treated successively with 2-methoxypropene, tetrabutylammonium fluoride, H_2-Pd/C,NalO_4, and diluted HCl to give D-2-deoxyribofuranose.2.(2S,3R,5S)-3,6-bis(benzyloxy)-5-tert-butyldimethylsiloxy-1,2-hexanediol was obtained using L-diethyl tartrate instead of D-diethyl tartrate in the method of 1.The vic-diol was treated successively Bu_4NF,NalO_4, and H_2-Pd/C to afford D-3-deoxyribofuranose.3.D-3-Azido-2,3-dideoxyribofuronose was prepared using NaN_3 instead of C_6H_5CH_2OH in the method of 1.4.D-2,3-Dideoxyribofuranose was obtained using LiAlH_4 instead of C_6H_5CH_2OH,on the other hand, L-2,3-dideoxyribofuranosewas produced by using(S)-glycidyl ether, L-diethyl tartrate, and LiAlH_4 according to the method of 1, respectively.5.According to the method of 1, D-2-deoxy-4-methylribofuranose and D-2-deoxy-3-methylribofuranose were obtained using of 1-methoxy-2-methyl-3-(phenylthio)-1-propene and 1-methoxy-3-(phenylthio)-1-butene, respectively.

1. 1-甲氧基-3-烯丙基阴离子与2，3-二氯-4-苯并咪唑反应，（E，S）-6-苄氧基-5-羟基-2-己烯醛经（a）叔丁基Me_2SiCl;（B）NaBH_4与D-酒石酸二乙酯经Sharpless-Katsuki不对称环氧化反应，再经C_6H_5CH_2OH处理，得到（2 R，3S，5S）-3，6-双苄氧基-5-叔丁基二甲基硅氧基-1，2-己二醇。该化合物依次与2-甲氧基丙烯、四丁基氟化铵、H_2-Pd/C、NaI O_4和稀盐酸反应得到D-2-脱氧呋喃核糖。(2S，3R，5S）-3，6-双以L-酒石酸二乙酯代替D-酒石酸二乙酯合成了5-叔丁基二甲基甲硅烷氧基-1，2-己二醇，再经Bu_4NF、NaIO_4、H_2-Pd/C处理得到D-3-脱氧呋喃核糖。用NaN_3代替1.4法中的C_6H_5CH_2OH得到3-二脱氧呋喃核糖;用LiAlH_4代替C_6H_5CH_2OH得到D-2，3-二脱氧呋喃核糖;根据1的方法，分别使用（S）-缩水甘油醚、L-酒石酸二乙酯和LiAlH_4制备3-二脱氧呋喃核糖。以1-甲氧基-2-甲基-3-甲基呋喃核糖为原料，分别合成了D-2-脱氧-4-甲基呋喃核糖和D-2-脱氧-3-甲基呋喃核糖。（苯硫基）-1-丙烯和1-甲氧基-3-（苯硫基）-1-丁烯。