3-C-(benzyloxymethyl)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose | 85315-67-9

• 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-C-(benzyloxymethyl)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose
• 英文别名: 1-O,2-O:5-O,6-O-Diisopropylidene-3-(benzyloxymethyl)-3-deoxy-alpha-D-allofuranose；(3aR,5S,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-(phenylmethoxymethyl)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 85315-67-9
• 化学式: C₂₀H₂₈O₆
• 分子量: 364.439
• InChiKey: LRPGZJJDHCKMST-UYTYNIKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-C-(benzyloxymethyl)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 在 sodium periodate 、 溶剂黄146 作用下， 生成
  参考文献：
  名称：

  构型刚性糖基作为潜在抗病毒剂的新型3'-DEOXY-3'-C-羟甲基核苷的合成

  摘要：

  基于氧杂环丁烷素A的扩环3'-C-羟甲基类似物表现出强大的抗病毒活性这一事实，将2'-羟基连接到4'-位置的两种构象刚性3'-C-羟甲基衍生物分别从1,2; 5,6-二-O-异亚丙基-D-葡萄糖开始合成或至6'-位。

  DOI：

  10.1081/ncn-100002354
• 作为产物：
  描述：

  O¹,O²;O⁵,O⁶-diisopropylidene-3-methylene-α-D-ribo-3-deoxy-hexofuranose 在 硼烷 作用下， 生成 3-C-(benzyloxymethyl)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose
  参考文献：
  名称：

  构型刚性糖基作为潜在抗病毒剂的新型3'-DEOXY-3'-C-羟甲基核苷的合成

  摘要：

  基于氧杂环丁烷素A的扩环3'-C-羟甲基类似物表现出强大的抗病毒活性这一事实，将2'-羟基连接到4'-位置的两种构象刚性3'-C-羟甲基衍生物分别从1,2; 5,6-二-O-异亚丙基-D-葡萄糖开始合成或至6'-位。

  DOI：

  10.1081/ncn-100002354

文献信息

• Phosphomolybdic Acid Supported on Silica Gel: An Efficient, Mild and Reusable Catalyst for the Chemoselective Hydrolysis of Acetonides
  作者：J. S. Yadav、S. Raghavendra、M. Satyanarayana、E. Balanarsaiah

  DOI：10.1055/s-2005-872701

  日期：——

  Carbohydrate acetonides were chemoselectively cleaved to the corresponding diols by using environmentally benign phosphomolybdic acid (H3PMo12O40) supported on silica gel (PMA-SiO2) at ambient temperature in a short span of 5-7 minutes in acetonitrile. Acid-labile protective groups such as THP, TBS, TBDPS, MOM, OMe and PMB were found to be stable under the reaction conditions.

  碳水化合物乙缩醛在环境友好的负载型磷钼酸（H3PMo12O40/硅胶，简称PMA-SiO2）作用下，于室温、乙腈溶液中仅需5至7分钟即可选择性地裂解为相应的二醇。在这种反应条件下，如THP、TBS、TBDPS、MOM、OMe和PMB等对酸不稳定的保护基团均能保持稳定。
• Synthesis and biological evaluation of thymine nucleosides fused with 3′,4′-tetrahydrofuran ring
  作者：Myong Jung Kim、Hea Ok Kim、Hee-Doo Kim、Joong Hyup Kim、Lak Shin Jeong、Moon Woo Chun

  DOI：10.1016/s0960-894x(03)00730-3

  日期：2003.10

  The pyrimidine nucleosides fused with 3',4'-tetrahydrofuran ring were successfully synthesized, starting from 1,2;5,6-di-O-isopropylidene-D-glucose and assayed for antiviral activities against HIV-1, HIV-2, EMCV, Cox. B3 and VSV. Thymine analogue (5) and its corresponding 2'-deoxy analogue (6) exhibited high cytotoxicity instead of giving antiviral activities.

  从1,2; 5,6-di-O-异亚丙基-D-葡萄糖开始，成功合成了与3'，4'-四氢呋喃环稠合的嘧啶核苷，并测定了其对HIV-1，HIV-2， EMCV，考克斯。B3和VSV。胸腺嘧啶类似物（5）及其相应的2'-脱氧类似物（6）表现出高细胞毒性，而不具有抗病毒活性。
• SYNTHESIS OF NOVEL 3′-DEOXY-3′-<i>C</i>-HYDROXYMETHYL NUCLEOSIDES WITH CONFORMATIONALLY RIGID SUGAR MOIETY AS POTENTIAL ANTIVIRAL AGENTS
  作者：Moon Woo Chun、Myung Jung Kim、Un Hee Jo、Joong Hyup Kim、Hee-Doo Kim、Lak Shin Jeong

  DOI：10.1081/ncn-100002354

  日期：2001.3.31

  Based on the fact that the ring expanded 3′-C-hydroxymethyl analogue of oxetanocin A exhibited potent antiviral activity, two types of conformationally rigid 3′-C-hydroxymethyl derivatives in which 2′-hydroxyl group is linked to the 4′-position or to the 6′-position were synthesized starting from 1,2;5,6-di-O-isopropylidene-D-glucose, respectively.

  基于氧杂环丁烷素A的扩环3'-C-羟甲基类似物表现出强大的抗病毒活性这一事实，将2'-羟基连接到4'-位置的两种构象刚性3'-C-羟甲基衍生物分别从1,2; 5,6-二-O-异亚丙基-D-葡萄糖开始合成或至6'-位。
• 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。