(+)-arabino-(4R,5S,6R)-hept-1-ene-4,5,6,7-tetrol 4,5,6,7-tetraacetate | 131484-45-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+)-arabino-(4R,5S,6R)-hept-1-ene-4,5,6,7-tetrol 4,5,6,7-tetraacetate
• 英文别名: 1,2,3,4-Tetra-O-acetyl-5,6,7-trideoxy-D-lyxo-6,7-heptenitol；[(2R,3S,4R)-2,3,4-triacetyloxyhept-6-enyl] acetate
• CAS: 131484-45-2
• 化学式: C₁₅H₂₂O₈
• 分子量: 330.335
• InChiKey: FGALFDJAGOFEPV-KFWWJZLASA-N

物化性质

• 沸点：
  361.3±31.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (+)-arabino-(4R,5S,6R)-hept-1-ene-4,5,6,7-tetrol 4,5,6,7-tetraacetate 在 potassium carbonate 二甲基硫 、 臭氧 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 2-Deoxy-D-glucose
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053
• 作为产物：
  描述：

  ribo-(4R,5R,6S)-5,6-epoxy-4-(1'-ethoxyethoxy)hept-1-en-7-ol 、 乙酸酐 以66%的产率得到
  参考文献：
  名称：

  ROUSH, WILLIAM R.;STRAUB, JULIE A.;VAN, NIEUWENHZA MICHAEL S., J. ORG. CHEM., 56,(1991) N, C. 1636-1648

  摘要：

  DOI：

文献信息

• Permanganate Oxidation Revisited: Synthesis of 3-Deoxy-2-uloses via Indium-Mediated Chain Elongation of Carbohydrates
  作者：Christoph Schmölzer、Michael Fischer、Walther Schmid

  DOI：10.1002/ejoc.201000623

  日期：2010.9

  Barbier-type indium-mediated allylation method to suitable substrates offers access to carbohydrates bearing a terminal olefin moiety. The C-C bond forming reaction generates a defined stereochemistry of the new chiral center and tolerates a wide variety of starting aldehydes thus allowing modifications in the carbohydrate backbone. Further transformations of the alkene moiety via an environmentally benign and

  将 Barbier 型铟介导的烯丙基化方法应用于合适的底物提供了获得带有末端烯烃部分的碳水化合物的途径。CC 键形成反应生成新手性中心的明确立体化学，并耐受多种起始醛，从而允许对碳水化合物主链进行修饰。通过使用高锰酸钾的环境良性和微妙的受控方案进一步转化烯烃部分，以良好的收率产生 3-deoxy-2-uloses 的结构基序。反应序列的最后部分侧重于对氧化步骤的成功至关重要的乙酰基的脱保护。目标分子的酸性和不稳定的 3-脱氧位置易于在标准脱乙酰化条件下消除，因此需要对分子进行衍生化。使用微波条件引入硫缩酮部分显示出有希望的结果，随后的标准转化适用于产生所需的产品。
• Tin- and indium-mediated allylation in aqueous media: application to unprotected carbohydrates
  作者：Enoch Kim、Dana M. Gordon、Walther Schmid、George M. Whitesides

  DOI：10.1021/jo00072a038

  日期：1993.9

  The convenient and efficient indium- and tin-mediated allylation method for extending the carbon chain of unprotected carbohydrates is illustrated by preparation of 4-6 and 9-10. Various 2-deoxyaldoses can be synthesized by the allylation of aldoses. Indium-mediated reactions between ethyl 2-(bromomethyl)acrylate and aldoses provide access to 2-keto-3-deoxyulosonic acids. These reactions are diastereoselective; the major product contains a threo relationship between the newly generated hydroxyl group and the C-2 hydroxyl group of the starting carbohydrate. Results obtained from reactions involving authentic organotin and organoindium reagents and from the corresponding heterogeneous reactions are similar.