Baer H H, Williams U, Radatus B
Department of Chemistry, University of Ottawa, Ontario, Canada.
Carbohydr Res. 1988 Mar 15;174:291-303. doi: 10.1016/0008-6215(88)85098-5.
Chemical reactions to open the cyclopropane ring in (1R)-1,2-dideoxy-3,4:5,6-di-O-isopropylidene-1,2-C-methylene-1-nitro-D-m annitol (1) were investigated. Catalytic hydrogenation over Pd-C produced the corresponding 1-amino compound, isolated as its N-acetyl derivative, but failed to cleave the ring. However, ring opening succeeded by nucleophilic addition of sodium thiophenoxide to 1, giving 1,2-dideoxy-3,4:5,6-di-O-isopropylidene-1-nitro-2-C- (phenylthio)methyl-D-mannitol. The latter reacted further with thiophenoxide to furnish phenyl 2-deoxy-3,4:5,6-di-O-isopropylidene-2-C-(phenylthio)methyl-D- mannothiohydroximate. Raney nickel converted both of these thio sugar derivatives into the same product, namely, 1-acetamido-1,2-dideoxy-3,4:5,6-di-O-isopropylidene-2-C-methyl-D-mannito l. The use of these transformations for the design of stereospecific syntheses of chiral isoalkyl structures is proposed.
研究了(1R)-1,2-二脱氧-3,4:5,6-二-O-异亚丙基-1,2-C-亚甲基-1-硝基-D-甘露糖醇(1)中开环丙烷环的化学反应。在Pd-C上进行催化氢化得到相应的1-氨基化合物，以其N-乙酰基衍生物形式分离出来，但未能开环。然而，通过苯硫酚钠对1进行亲核加成成功开环，得到1,2-二脱氧-3,4:5,6-二-O-异亚丙基-1-硝基-2-C-(苯硫基)甲基-D-甘露糖醇。后者与苯硫酚进一步反应生成苯基2-脱氧-3,4:5,6-二-O-异亚丙基-2-C-(苯硫基)甲基-D-甘露硫肟酸酯。雷尼镍将这两种硫代糖衍生物都转化为同一产物，即1-乙酰氨基-1,2-二脱氧-3,4:5,6-二-O-异亚丙基-2-C-甲基-D-甘露糖醇。提出了利用这些转化来设计手性异烷基结构的立体专一合成方法。
