3-deoxy-3-C-benzyloxymethyl-1,2-O-isopropylidine-5-methylene-α-D-ribo-hexofuranose | 85315-74-8

• 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: 3-deoxy-3-C-benzyloxymethyl-1,2-O-isopropylidine-5-methylene-α-D-ribo-hexofuranose
• 英文别名: 3-C-(benzyloxymethyl)-3,5,6-trideoxy-1,2-O-isopropylidene-α-D-ribo-5-hexenofuranose；(3aR,5R,6R,6aR)-5-ethenyl-2,2-dimethyl-6-(phenylmethoxymethyl)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 85315-74-8
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: KRYIPVQLKAUVOX-KLHDSHLOSA-N

物化性质

• 沸点：
  365.1±37.0 °C(Predicted)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  3-deoxy-3-C-benzyloxymethyl-1,2-O-isopropylidine-5-methylene-α-D-ribo-hexofuranose 在 amberlyst IR-120 (H⁺) resin 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以88%的产率得到methyl-2-hydroxy-3-deoxy-3-C-benzyloxymethyl-5-methylene-α-D-ribo-hexofuranoside
  参考文献：
  名称：

  Towards the enantioselective synthesis of anti-HIV agents litseaverticillols C and K from d-glucose

  摘要：

  The first enantioselective synthesis towards the litseaverticillols C and K has been achieved, from D-glucose, using the ring closing metathesis (RCM) and Wittig reactions as key steps. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.01.037
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-α-D-ribo-3-hexulofuranose 在 dimethyl sulfide borane 、 硫酸 、 sodium hydride 、 sodium amide 、 sodium iodide 、 锌 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 41.5h， 生成 3-deoxy-3-C-benzyloxymethyl-1,2-O-isopropylidine-5-methylene-α-D-ribo-hexofuranose
  参考文献：
  名称：

  Towards the enantioselective synthesis of anti-HIV agents litseaverticillols C and K from d-glucose

  摘要：

  The first enantioselective synthesis towards the litseaverticillols C and K has been achieved, from D-glucose, using the ring closing metathesis (RCM) and Wittig reactions as key steps. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.01.037

文献信息

• Synthesis of a phosphinic acid analogue of cyclic AMP
  作者：Andrew C. Regan、Nunzio Sciammetta、Peter I. Tattersall

  DOI：10.1016/s0040-4039(00)01437-4

  日期：2000.10

  Synthesis of a cyclic phosphinate ester analogue of cyclic AMP was achieved by using a double Arbuzov-type cyclisation of bis-trimethylsilyl phosphonite onto a sugar dihalide derivative as the key step.

  通过将双三甲基甲硅烷基亚膦酸酯在糖二卤化物衍生物上的双Arbuzov型环化作为关键步骤，可以实现环状AMP的环状次膦酸酯类似物的合成。
• Synthetic Studies of Rifamycins. V. A Chiral Synthesis of an Ansa-chain Compound for the C-17–C-29 Portion of Rifamycin W
  作者：Masaya Nakata、Hiroyuki Enari、Mitsuhiro Kinoshita

  DOI：10.1246/bcsj.55.3283

  日期：1982.10

  The chiral synthesis of methyl 5,7,9-tri-O-acetyl-2-C-(acetoxymethyl)-2,4,6,8,10,11,12-heptadeoxy-4,6,8,10-tetra-C-methyl-aldehydo-l-glycero-l-talo-l-manno-(E)-11-tridecenuronate 1-(dimethyl acetal) (III), a useful synthetic segment for the C-17-C-29 portion of rifamycin W, is described. The key intermediate, 3-O-(t-butyldimethylsilyl)-2,4,7-trideoxy-5,6-O-isopropylidene-2,4-di-C-methyl-aldehydo-d-glycero-d-talo-heptose (28) was synthesized in 30% yield from methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-α-d-glucopyranoside in 15 steps. The synthesis involves key steps of highly stereoselective Grignard reaction and regiospecific cis-epoxide ring-opening reaction. The condensation of 28 with 3,3-diethoxy-2-lithio-1-propene afforded about 1.6:1 excess of the “Cram” product (30, 56% yield). The desilylation of 30 followed by homogeneous hydrogenation with (Ph3P)3RhCl gave only the erythro product 34. 3,5-Di-O-benzyl-2,4,6-trideoxy-2,4,6-tri-C-methyl-l-glycero-l-manmo-heptodialdose 1-(diethyl acetal) derived from 34, condensed with the lithium reagent prepared (in ether at −95–−90 °C) from butyllithium and 3-C-(benzyloxymethyl)-3,5,6-trideoxy-5-iodo-1,2-O-isopropylidene-α-d-hexenofuranose, derived from 3-deoxy-3-C-hydroxymethyl-1,2 : 5,6-di-O-isopropylidene-α-d-allofuranose, to afford a 4 : 1 mixture of the “Cram” product and its epimer in 80% yield. The homogeneous hydrogenation of the mixture followed by the debenzylation gave the diastereomerically pure major product, which could be transformed into III in 6 steps.

  本文介绍了 5,7,9-三-O-乙酰基-2-C-（乙酰氧甲基）-2,4,6,8,10,11,12-庚二氧基-4,6,8,10-四-C-甲基-aldehydo-l-甘油-l-talo-l-manno-(E)-11-十三烯脲酸甲酯 1-（二甲基乙缩醛）(III)的手性合成，这是利福霉素 W 的 C-17-C-29 部分的有用合成片段。关键中间体 3-O-(叔丁基二甲基硅烷基)-2,4,7-三脱氧-5,6-O-异亚丙基-2,4-二-C-甲基-醛基-d-缩水甘油-d-庚糖 (28) 是由甲基 4,6-O-亚苄基-3-脱氧-3-C-甲基-α-d-吡喃葡萄糖苷经 15 个步骤合成的，收率为 30%。合成的关键步骤包括高度立体选择性的格氏反应和区域特异性的顺式环氧化物开环反应。28 与 3,3-二乙氧基-2-二硫代-1-丙烯缩合后，可得到过量的 "Cram "产物（30，产率 56%），过量率约为 1.6:1。对 30 进行脱硅处理，然后用 (Ph3P)3RhCl 进行均相氢化，只得到赤式产物 34。由 34 生成的 3,5-二-O-苄基-2,4,6-三脱氧-2,4,6-三-C-甲基-l-甘油-l-芒诺-庚二缩醛 1-（二乙基缩醛）、与丁锂和 3-C-(苄氧基甲基)-3,5,6-三脱氧-5-碘-1,2-O-异亚丙基-α-d-己烯呋喃糖制备的锂试剂（在乙醚中，-95-90 °C）缩合，该试剂由 3-deoxy-3-C-hydroxymethyl-1,2 ：5,6-二-O-异亚丙基-α-d-异呋喃糖，得到 4 : 1 的 "Cram "产品及其表聚物混合物，收率为 80%。对混合物进行均相氢化，然后进行去苄基化反应，得到非对映纯的主要产物，该产物可通过 6 个步骤转化为 III。
• Zirconium-mediated ring contraction: An efficient synthesis of enantiomerically pure key intermediate of carbocyclic oxetanocin
  作者：Hisanaka Ito、Takeo Taguchi、Yuji Hanzawa

  DOI：10.1016/s0040-4039(00)60421-5

  日期：1993.11

  A key intermediate 3b of carbocyclic oxetanocin analogues (COXTs) 2 was prepared from 4-vinylfuranoside derivative by zirconium-mediated ring contraction.

  由4-乙烯基呋喃糖苷衍生物通过锆介导的环收缩制得碳环氧杂环丁烷类似物（COXTs）2的关键中间体3b。
• Towards the enantioselective synthesis of anti-HIV agents litseaverticillols C and K from d-glucose
  作者：Debendra K. Mohapatra、Dhananjoy Mondal、Mukund K. Gurjar

  DOI：10.1016/j.tet.2007.01.037

  日期：2007.3

  The first enantioselective synthesis towards the litseaverticillols C and K has been achieved, from D-glucose, using the ring closing metathesis (RCM) and Wittig reactions as key steps. (c) 2007 Elsevier Ltd. All rights reserved.