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

1.1-甲氧基-3-(苯硫基)-1-丙烯衍生的烯丙基阴离子与苯基(R)-缩水甘油醚的反应(E，S)-6-苄氧基-5-羟基-2-己烯醛，然后分两步转化为(E，S)-6-benzyloxy-5-tert-butyldimethylsiloxy-2-hexen-1-ol)：(A)叔丁Me_2SiCl；(B)D-酒石酸二乙酯与NaBH_4的不对称环氧化反应，然后用C_6H_5CH_2OH afforded(2R，3S，5S)-3，6-bis(benzyloxy)-5-tert-butyldimethylsiloxy-1，2-hexanediol.处理该化合物经2-甲氧基丙烯、四丁基氟化铵、H_2-Pd/C、NaLO_4处理后，用L酒石酸二乙酯代替D-酒石酸二乙酯得到D-2-deoxyribofuranose.2.(2S，3R，5S)-3，6-bis(benzyloxy)-5-tert-butyldimethylsiloxy-1，2-hexanediol。用NaN_3代替C_6H_5CH_2OH以1.4的方法制备了制备D-3-deoxyribofuranose.3.D-3-Azido-2，3-dideoxyribofuronose的H_2-Pd/C。用LiAlH_4代替C_6H_5CH_2OH制备了D-2，3-二脱氧核呋喃糖。另一方面，用(S)-缩水甘油醚、L-酒石酸二乙酯和LiAlH_4分别按1的方法合成了D-2，3-二脱氧核糖呋喃糖。以1-甲氧基-2-甲基-3-(苯硫基)-1-丙烯和1-甲氧基-3-(苯硫基)-1-丁烯为原料，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。

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.