5,6,7,8,9-Pentadeoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-non-8-enofuranose | 163185-16-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,6,7,8,9-Pentadeoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-non-8-enofuranose
• 英文别名: (3aR,6S,6aR)-6-(benzyloxy)-2,2-dimethyl-5-(pent-4-enyl)tetrahydrofuro[2,3-d][1,3]dioxole；(3aR,5R,6S,6aR)-2,2-dimethyl-5-pent-4-enyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 163185-16-8
• 化学式: C₁₉H₂₆O₄
• 分子量: 318.413
• InChiKey: DRFSCOICSFMMRO-XMTFNYHQSA-N

物化性质

• 沸点：
  394.9±42.0 °C(predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,6,7,8,9-Pentadeoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-non-8-enofuranose 在 iodonium(di-γ-collidine) perchlorate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.17h， 生成 (5R)-5-[(S)-[(2R)-6-(iodomethyl)oxan-2-yl]-phenylmethoxymethyl]-2,2-dimethyl-1,3-dioxolan-4-ol
  参考文献：
  名称：

  1,2-O-Isopropylidenefuranose Templates for the Synthesis of Complex Cyclic Ethers via Neighboring Group Participation by the Acetal Ring Oxygen

  摘要：

  Novel strategies are described for the direct transformation of C5-allylated-1,2-O-isopropylidene-furanoses into complex cyclic ethers. Reaction of these substrates with iodonium ion under aqueous conditions resulted in the facile formation of 2,5-disubstituted tetrahydrofurans (THF's) containing highly substituted branches, in good to high yields, albeit with modest cis stereoselectivity. A similar result was obtained for the one case of the analogous tetrahydropyran (THP) system that was examined. These reactions presumably proceed via neighboring group participation by the acetal ring oxygen on an iodonium ion-alkene charge transfer complex to give a cyclic oxonium ion, thence a cyclic ether-oxocarbenium ion which undergoes intermolecular capture by water. Under anhydrous conditions, substrates which contained a 3-0-(2'-methyl-2'-buten-4'-yl) substituent led to high yields of adjacently connected THF-THP or THP-THP structures. These products are explainable in terms of a two-step process in which a cyclic ether-oxocarbenium ion, resulting from the initial participation reaction, undergoes nucleophilic capture by the activated alkene. A notable feature of this reaction was that only a single THP isomer was obtained in the second ring forming reaction, presumably a consequence of the cyclic nature of the oxocarbenium ion derived from the 1,2-O-isopropylidene acetal residue.

  DOI：

  10.1021/jo00105a012
• 作为产物：
  描述：

  5,6,7,8-Tetradeoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-oct-7-enofuranose 在 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 草酰氯 、 双氧水 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 8.92h， 生成 5,6,7,8,9-Pentadeoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-non-8-enofuranose
  参考文献：
  名称：

  1,2-O-Isopropylidenefuranose Templates for the Synthesis of Complex Cyclic Ethers via Neighboring Group Participation by the Acetal Ring Oxygen

  摘要：

  Novel strategies are described for the direct transformation of C5-allylated-1,2-O-isopropylidene-furanoses into complex cyclic ethers. Reaction of these substrates with iodonium ion under aqueous conditions resulted in the facile formation of 2,5-disubstituted tetrahydrofurans (THF's) containing highly substituted branches, in good to high yields, albeit with modest cis stereoselectivity. A similar result was obtained for the one case of the analogous tetrahydropyran (THP) system that was examined. These reactions presumably proceed via neighboring group participation by the acetal ring oxygen on an iodonium ion-alkene charge transfer complex to give a cyclic oxonium ion, thence a cyclic ether-oxocarbenium ion which undergoes intermolecular capture by water. Under anhydrous conditions, substrates which contained a 3-0-(2'-methyl-2'-buten-4'-yl) substituent led to high yields of adjacently connected THF-THP or THP-THP structures. These products are explainable in terms of a two-step process in which a cyclic ether-oxocarbenium ion, resulting from the initial participation reaction, undergoes nucleophilic capture by the activated alkene. A notable feature of this reaction was that only a single THP isomer was obtained in the second ring forming reaction, presumably a consequence of the cyclic nature of the oxocarbenium ion derived from the 1,2-O-isopropylidene acetal residue.

  DOI：

  10.1021/jo00105a012

文献信息

• Total synthesis of (+)-lentiginosine from d-glucose
  作者：Mohammad Abrar Alam、Yashwant D. Vankar

  DOI：10.1016/j.tetlet.2008.07.057

  日期：2008.9

  A total synthesis of (+)-lentiginosine, a potent and selective amyloglucosidase inhibitor, is reported from a d-glucose-derived epoxide in 38% overall yield. In this synthesis, ambient conditions and readily available starting materials and reagents are used.

  从d-葡萄糖衍生的环氧化物报道了（+）-龙胆草碱的全合成，这是一种有效的和选择性的淀粉葡糖苷酶抑制剂，总产率为38％。在该合成中，使用环境条件和容易获得的起始原料和试剂。
• 1,2-O-Isopropylidenefuranose Templates for the Synthesis of Complex Cyclic Ethers via Neighboring Group Participation by the Acetal Ring Oxygen
  作者：Weifang Shan、Phyllis Wilson、Wei Liang、David R. Mootoo

  DOI：10.1021/jo00105a012

  日期：1994.12

  Novel strategies are described for the direct transformation of C5-allylated-1,2-O-isopropylidene-furanoses into complex cyclic ethers. Reaction of these substrates with iodonium ion under aqueous conditions resulted in the facile formation of 2,5-disubstituted tetrahydrofurans (THF's) containing highly substituted branches, in good to high yields, albeit with modest cis stereoselectivity. A similar result was obtained for the one case of the analogous tetrahydropyran (THP) system that was examined. These reactions presumably proceed via neighboring group participation by the acetal ring oxygen on an iodonium ion-alkene charge transfer complex to give a cyclic oxonium ion, thence a cyclic ether-oxocarbenium ion which undergoes intermolecular capture by water. Under anhydrous conditions, substrates which contained a 3-0-(2'-methyl-2'-buten-4'-yl) substituent led to high yields of adjacently connected THF-THP or THP-THP structures. These products are explainable in terms of a two-step process in which a cyclic ether-oxocarbenium ion, resulting from the initial participation reaction, undergoes nucleophilic capture by the activated alkene. A notable feature of this reaction was that only a single THP isomer was obtained in the second ring forming reaction, presumably a consequence of the cyclic nature of the oxocarbenium ion derived from the 1,2-O-isopropylidene acetal residue.