(3aS,4R,5R,6S,7R,7aR)-5,6,7-Tris-benzyloxy-2,2-dimethyl-hexahydro-benzo[1,3]dioxol-4-ol | 131233-63-1

• 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: (3aS,4R,5R,6S,7R,7aR)-5,6,7-Tris-benzyloxy-2,2-dimethyl-hexahydro-benzo[1,3]dioxol-4-ol
• 英文别名: (3aS,4R,5R,6S,7R,7aR)-2,2-dimethyl-5,6,7-tris(phenylmethoxy)-3a,4,5,6,7,7a-hexahydro-1,3-benzodioxol-4-ol
• CAS: 131233-63-1
• 化学式: C₃₀H₃₄O₆
• 分子量: 490.596
• InChiKey: WORUQUKKISUTQP-LQZPZKLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3aS,4R,5R,6S,7R,7aR)-5,6,7-Tris-benzyloxy-2,2-dimethyl-hexahydro-benzo[1,3]dioxol-4-ol 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 氢气 、 三氧化硫吡啶 、 三乙胺 作用下， 以 甲醇 、 乙醇 、 溶剂黄146 、 二甲基亚砜 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 26.42h， 生成 epi-Inositol
  参考文献：
  名称：

  衍生自（±）-3,4,5-三-O-苄基-1,2-O-异亚丙基-肌醇的酮的反应：表肌醇和4-C-甲基-外消旋衍生物的制备表-[（±）-异米醇]和4-C-甲基-肌醇[（±）-米醇]

  摘要：

  摘要用吡啶-SO3络合物在甲基亚砜中氧化（±）-3,4,5-三-O-苄基-1,2-O-异亚丙基-肌醇-丁酮几乎仅是相应的表肌醇衍生物。酮与重氮甲烷反应生成环氧化物，用氢化铝锂还原该环氧化物得到4-C-甲基-肌醇衍生物，酮与甲基碘化镁的反应得到异构体4-C-甲基-表肌醇衍生物。

  DOI：

  10.1016/s0008-6215(96)00330-8
• 作为产物：
  描述：

  (±)-1,2:5,6-di-O-isopropylidene-myo-inositol 在 3 A molecular sieve 、 四丁基溴化铵 、 水 、 sodium hydride 、 二正丁基氧化锡 、 对甲苯磺酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， 反应 1.58h， 生成 (3aS,4R,5R,6S,7R,7aR)-5,6,7-Tris-benzyloxy-2,2-dimethyl-hexahydro-benzo[1,3]dioxol-4-ol
  参考文献：
  名称：

  The synthesis and resolution of (±)-1,5,6-tri-O-benzyl-myo-inositol

  摘要：

  Racemic 1,5,6-tri-O-benzyl-myo-inositol was prepared by five routes and converted into 1,5,6-tri-O-benzyl-2,3-O-isopropylidene-myo-inositol, the camphanates of which were readily separated by chromatography. The absolute configurations of the chiral derivatives were established by their conversion into the known chiral 1,4,5,6-tetra-O-benzyl-myo-inositols. 1D-1,5,6-Tri-O-benzyl-2,3-O-isopropylidene-myo-inositol was converted into 1D-1,3,5,6-tetra-O-benzyl-myo-inositol and thence into 1D-2,4-di-O-methyl-myo-inositol. 1D-1,5,6-Tri-O-benzyl-myo-inositol was converted into 1D-1,2,5,6-tetra-O-benzyl-myo-inositol, the diacetate of which is a chiral analogue of "thermosalient crystals". The potential of the above compounds for the synthesis of natural products is surveyed.

  DOI：

  10.1016/0008-6215(90)80132-m

文献信息

• Nickel-Catalyzed Stereoselective Glycosylation with C(2)-<i>N</i>-Substituted Benzylidene <scp>d</scp>-Glucosamine and Galactosamine Trichloroacetimidates for the Formation of 1,2-<i>cis</i>-2-Amino Glycosides. Applications to the Synthesis of Heparin Disaccharides, GPI Anchor Pseudodisaccharides, and α-GalNAc
  作者：Enoch A. Mensah、Fei Yu、Hien M. Nguyen

  DOI：10.1021/ja106682m

  日期：2010.10.13

  α-selectivity. The reactive sites of the nucleophiles or the nature of the protecting groups have little effect on the α-selectivity. This methodology has also been successfully applied to both disaccharide donors and acceptors to provide the corresponding oligosaccharides in high yields and α-selectivity. The efficacy of the nickel procedure has been further applied toward the preparation of heparin disaccharides

  1,2-cis-2-amino glycosides 是在各种生物学上重要的寡糖和糖肽中发现的关键成分。尽管 1,2-cis-2-氨基糖苷的合成取得了显着进展，但目前最先进方法的缺点包括底物范围有限、产率低、反应时间长和异头混合物。我们开发了一种通过镍催化的 α-选择性糖基化与 C(2)-N-取代的亚苄基 D-葡糖胺和半乳糖胺三氯乙酰亚胺合成 1,2-顺-2-氨基糖苷的新方法。这些糖基供体能够与多种醇偶联，以高产率提供具有出色 α 选择性的糖缀合物。此外，仅需要亚化学计量的镍 (5-10 mol%) 才能在 25 °C 下进行反应。目前的镍方法依赖于镍配体配合物的性质来控制 α 选择性。亲核试剂的反应位点或保护基团的性质对α-选择性几乎没有影响。该方法也已成功应用于二糖供体和受体，以高产率和 α 选择性提供相应的寡糖。镍过程的功效已进一步应用于制备肝素二糖、GPI 锚定假二糖和 α-Glu
• Synthesis of optically active myo-inositol derivatives starting from phytic acid
  作者：Corinne Blum、Nicola Rehnberg、Bernard Spiess、Gilbert Schlewer

  DOI：10.1016/s0008-6215(97)00131-6

  日期：1997.8

  Abstract Phytic acid treated with Baker's yeast gave d -myo-inositol-1,2,6-tris(phosphate) (α-trinositol) which was transformed into (+)- d -1,2-O- isopropylidene -myo- inositol and (−)- d -3,4,5- tri -O- benzyl -myo- inositol , two key intermediates in the synthesis of optically active myo-inositol derivatives and related compounds.

  摘要用贝克酵母处理过的植酸得到d-肌醇-1,2-，6-三（磷酸）（α-三糖醇），然后转化为（+）-d-1,2-O-异亚丙基-肌醇和（-）-d -3,4,5-三-O-苄基-肌醇，这是光学活性肌醇衍生物和相关化合物合成中的两个关键中间体。
• Strategies for stereocontrol at C1 or C2 in syntheses of α‐glucosaminides
  作者：Bert Fraser‐Reid、G. Anilkumar、Latha G. Nair、Lars Olsson、Mercedes Garcia Martin、Jacquitta K. Daniels

  DOI：10.1560/kdp7-d0ba-bn04-3h3a

  日期：2000.12

  The C1 and C2 stereocenters of α‐glucosaminides can be prepared by establishing the stereocenters in either order. For the former, a C2‐azido glucosyl donor is prepared first, and the restraining effect of a 4,6‐O‐benzylidene ring is used to induce α‐coupling. For the latter, the C1 linkage is prepared first by use of an n‐pentenyl‐manno‐1,2‐orthoester donor which ensures (a) clean α‐coupling and (b) a convenient C2‐ester. The C2‐ester is replaced with a triflate leaving group, and nucleophilic displacement is effected by use of a hypervalent silicon azide.

  摘要 α-氨基葡萄糖苷的 C1 和 C2 立体中心可以按两种顺序制备。对于前者，首先制备 C2-叠氮葡萄糖基供体，然后利用 4,6-O-亚苄基环的限制作用诱导 α-偶联。对于后者，首先使用正戊烯基-甘露-1,2-正酯供体制备 C1 连接，以确保 (a) α 偶联干净利落，(b) C2- 酯方便使用。C2- 酯被三酸酯离去基团取代，并通过使用超价叠氮化硅实现亲核置换。
• Efficient syntheses of chiral myo-inositol derivatives—key intermediates in glycosylphosphatidylinositol (GPI) syntheses
  作者：Fei Yu、Zhongwu Guo

  DOI：10.1016/j.bmcl.2009.03.151

  日期：2009.7

  A facile and effective method was developed for large-scale syntheses of myo-inositol derivatives with the 1,2,6-O-positions differentiated from each other and from other positions as well. The syntheses started from methyl alpha-D-glucopyranoside, and the key steps are Ferrier rearrangement and a series of other regioselective and stereoselective reactions. The target compounds are key intermediates in the synthesis of GPIs. (C) 2009 Elsevier Ltd. All rights reserved.
• The alkylation of dibutylstannylene derivatives of 1,2-O-isopropylidene-myo-inositol.
  作者：Jill Gigg、Roy Gigg、Eloisa Martin-Zamora

  DOI：10.1016/s0040-4039(00)73573-8

  日期：1993.4

  Benzylation (or allylation) of 1,2-O-isopropylidene-myo-inositol in the presence of an excess of dibutyltin oxide gives, as major products, the readily isolable 3,4,6- (12) and 3,5,6-tri-O-alkyl (13) derivatives which are valuable intermediates for the synthesis of inositol phosphates of the phosphatidylinositol cycle.