ethyl 2,6-anhydro-3-deoxy-8,9-O-isopropylidene-7-O-(methoxymethyl)-D-glycero-D-talo-non-4-ulosonate | 287119-27-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,6-anhydro-3-deoxy-8,9-O-isopropylidene-7-O-(methoxymethyl)-D-glycero-D-talo-non-4-ulosonate
• 英文别名: ethyl (2S,5S,6R)-6-[(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-(methoxymethoxy)methyl]-5-hydroxy-4-oxooxane-2-carboxylate
• CAS: 287119-27-1
• 化学式: C₁₆H₂₆O₉
• 分子量: 362.377
• InChiKey: OEXXBNCGHNEKLX-RYMFRWLXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  ethyl 2,6-anhydro-3-deoxy-8,9-O-isopropylidene-7-O-(methoxymethyl)-D-glycero-D-talo-non-4-ulosonate 在 吡啶 、 1,3-丙二硫醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (2S,4S,5R,6S)-4,5-Diacetoxy-6-((1R,2R)-1,2,3-trihydroxy-propyl)-tetrahydro-pyran-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Enantioselective Synthesis of Ethyl 4,5,7,8,9-Penta-O-acetyl-2,6-anhydro- 3-deoxy-D-erythro-L-gluca-nononate: a 2-Monodeoxygenated Derivative of `2-Keto-3-deoxy-D-glycero-D-galacto-nononic Acid'

  摘要：

  A study aimed at developing an enantioselective synthesis of the title compound 23, a 2-monodeoxy analogue of;he naturally occurring (+)-2-keto-3-deoxy-D-glycero-D-galacto-2-nononic acid (KDN),is reported. From D-mannose as starting material, the chiral 1,3-diene 10, activated by a silyloxy substituent at C(2), was prepared in six steps (Scheme I). However, the intermediates were often contaminated with varying amounts of by-products arising from overoxidation during cleavage with periodic acid. An alternative route starting from the inexpensive and readily available D-isoascorbic acid (12), though a little longer than the first, satisfactorily circumvented the purification problem and led to the desired dienes 17 in good yields (scheme2). The [Co-II(S.S)-(+)-salen]-catalyzed hetero-Diels-Alder reactions of the aforementioned dienes with ethyl glyoxylate proceeded smoothly at room temperature, giving the dihydropyrano adducts 18 in moderate yields (Scheme 3). Dihydroxylation of 18a followed by reduction of the keto function gave the desired 4,5-trans dihydroxy moiety of the KDN framework (Scheme 4, see 21). The spectroscopic data of the penta-O-acetylated 2-deoxy-KDN ethyl ester 23 were consistent with those reported for the corresponding methyl ester derived from natural KDN.

  DOI：

  10.1002/(sici)1522-2675(20000510)83:5<943::aid-hlca943>3.0.co;2-h
• 作为产物：
  描述：

  ethyl 2,6-anhydro-4-O-[(tert-butyl)dimethylsilyl]-3,5-dideoxy-8,9-O-isopropylidene-7-O-(methoxymethyl)-D-manno-non-4-enonate 在 K2 N-甲基吲哚酮 作用下， 以 水 、 丙酮 为溶剂， 生成 ethyl 2,6-anhydro-3-deoxy-8,9-O-isopropylidene-7-O-(methoxymethyl)-D-glycero-D-talo-non-4-ulosonate 、 (2S,5R,6R)-6-[(R)-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-methoxymethoxy-methyl]-5-hydroxy-4-oxo-tetrahydro-pyran-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Enantioselective Synthesis of Ethyl 4,5,7,8,9-Penta-O-acetyl-2,6-anhydro- 3-deoxy-D-erythro-L-gluca-nononate: a 2-Monodeoxygenated Derivative of `2-Keto-3-deoxy-D-glycero-D-galacto-nononic Acid'

  摘要：

  A study aimed at developing an enantioselective synthesis of the title compound 23, a 2-monodeoxy analogue of;he naturally occurring (+)-2-keto-3-deoxy-D-glycero-D-galacto-2-nononic acid (KDN),is reported. From D-mannose as starting material, the chiral 1,3-diene 10, activated by a silyloxy substituent at C(2), was prepared in six steps (Scheme I). However, the intermediates were often contaminated with varying amounts of by-products arising from overoxidation during cleavage with periodic acid. An alternative route starting from the inexpensive and readily available D-isoascorbic acid (12), though a little longer than the first, satisfactorily circumvented the purification problem and led to the desired dienes 17 in good yields (scheme2). The [Co-II(S.S)-(+)-salen]-catalyzed hetero-Diels-Alder reactions of the aforementioned dienes with ethyl glyoxylate proceeded smoothly at room temperature, giving the dihydropyrano adducts 18 in moderate yields (Scheme 3). Dihydroxylation of 18a followed by reduction of the keto function gave the desired 4,5-trans dihydroxy moiety of the KDN framework (Scheme 4, see 21). The spectroscopic data of the penta-O-acetylated 2-deoxy-KDN ethyl ester 23 were consistent with those reported for the corresponding methyl ester derived from natural KDN.

  DOI：

  10.1002/(sici)1522-2675(20000510)83:5<943::aid-hlca943>3.0.co;2-h