作者:R.W. Lowe、W.A. Szarek、J.K.N. Jones
DOI:10.1016/s0008-6215(00)82783-4
日期:1973.6
general protocol for the conversion of 2-hexuloses into 3-heptuloses is illustrated by the synthesis of D - manno -3-heptulose ( 9 ) from D -fructose ( 1 ). Oxidation of 2,3:4,5-di- O -isopropylidene-β- D -fructopyranose ( 2 ) with the Pfitzner-Moffatt reagent gave, in high yield, 2,3:4,5-di- O -isopropylidene-β- D - arabino -hexosulo-2,6-pyranose ( 3 ), which was converted into the unsaturated sugar 4
摘要用D-果糖(1)合成D-manno -3-庚糖(9)阐明了将2-己糖转化为3-庚糖的一般方案。用Pfitzner-Moffatt试剂氧化2,3:4,5-二-O-异亚丙基-β-D-果糖基吡喃糖(2),高收率得到2,3:4,5-二-O-异亚丙基- β-D-阿拉伯糖-己基-2,6-吡喃糖(3),通过与亚甲基三苯基膦烷反应转化为不饱和糖4。将三氟乙酸碘加到4中,然后将所得的加合物5脱酰基,得到结晶的2-脱氧-2-碘-3,4:5,6-二-O-异亚丙基-β-D-葡萄糖-3 -heptulos-3,7-吡喃糖(6)。用氢氧化钠处理碘代醇6得到环氧化物7,通过进一步用氢氧化钠处理,将其转化为3,4:5,6-二-O-异亚丙基-β-D-甘露聚糖-3-庚酮-3,7-吡喃糖(8)。二醇8的酸催化水解提供了D-甘露聚糖-3-庚糖(9)。