1,2,3-trideoxy-L-arabino-oct-1-enitol | 195196-46-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 1,2,3-trideoxy-L-arabino-oct-1-enitol
• 英文别名: (2R,3R,4R)-oct-7-ene-1,2,3,4,5-pentol
• CAS: 195196-46-4
• 化学式: C₈H₁₆O₅
• 分子量: 192.212
• InChiKey: ZMFLKZINFYQUJM-UIYHXYAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.8
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  101
• 氢给体数：
  5
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 1,2,3-trideoxy-L-arabino-oct-1-enitol 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 16.0h， 以670 mg的产率得到1,2,3,4,5-penta-O-acetyl-6,7,8-trideoxy-L-gulo-7-octenitol
  参考文献：
  名称：

  碳水化合物合成中的铟介导烯丙基化：一种获得更高 2-乙酰氨基-2-脱氧糖的简短而有效的方法。

  摘要：

  高级氨基糖是碳水化合物合成中有趣的目标，因为这些化合物在生物系统中起着重要作用。然而，它们从天然来源的可用性是有限的。因此，为了研究它们的生物学功能，开发此类化合物的简便且适应性强的路线至关重要。我们对这些目标分子的合成路线利用容易获得的戊糖和己糖，它们受到铟介导的双碳链伸长。随后的臭氧分解和碱处理产生 α、β-不饱和醛，使用 Jorgenson 协议将其立体选择性环氧化。在 Wittig 链延长后，所得烯丙基环氧化物在钯催化下用叠氮化三甲基甲硅烷进行区域和立体选择性打开。最后，建立了合适的脱保护方案，从酸性乙酸盐裂解和臭氧分解开始。产物的过乙酰化简化了纯化，随后的叠氮化物还原，然后使用甲醇甲醇钠进行最终脱乙酰化，得到标题化合物。

  DOI：

  10.3762/bjoc.10.231
• 作为产物：
  描述：

  L-阿拉伯糖 、 二烯丙基二溴锡 以 水 为溶剂， 以84%的产率得到1,2,3-trideoxy-L-arabino-oct-1-enitol
  参考文献：
  名称：

  Organometallic Reactions in Aqueous Media. The Nature of the Organotin Intermediate in the Tin-Mediated Allylation of Carbonyl Compounds

  摘要：

  Allyl bromide and tin reacted in aqueous media to give first allyltin(II) bromide (5) and then diallyltin dibromide (4). Either organotin intermediate can react with carbonyl compounds to give the corresponding homoallylic alcohols. Competitive experiment showed that 5 was more reactive than 4.

  DOI：

  10.1021/jo9901337

文献信息

• Use of an Organometallic Reagent in Water: Sc(OTf)₃-Catalyzed Allylation Reactions of Aldehydes in Micellar Systems
  作者：Shu Kobayashi、Takeshi Wakabayashi、Hidekazu Oyamada

  DOI：10.1246/cl.1997.831

  日期：1997.8

  The Sc(OTf)3-catalyzed allylation reactions of aldehydes with tetraallyltin proceeded smoothly in micellar systems to afford the corresponding homoallylic alcohols in high yields. The reactions were successfully carried out in the presence of a small amount of a surfactant in water without using any organic solvents.

  Sc(OTf)3 催化的醛与四烯丙基锡的烯丙基化反应在胶束体系中顺利进行，以高产率得到相应的高烯丙醇。该反应在少量表面活性剂的存在下成功进行，不使用任何有机溶剂。
• 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。
• Aqueous reactions with a Lewis acid and an organometallic reagent. The scandium trifluoromethanesulfonate-catalyzed allylation reaction of carbonyl compounds with tetraallyltin
  作者：Iwao Hachiya、Shu Kobayashi

  DOI：10.1021/jo00077a009

  日期：1993.12

  The allylation reaction of a wide variety of carbonyl compounds with tetraallyltin was successfully carried out in aqueous media by using scandium trifluoromethanesulfonate (scandium triflate) as a catalyst.
• 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.
• Addition of Allylindium Reagents to Aldehydes Substituted at C_α or C_β with Heteroatomic Functional Groups. Analysis of the Modulation in Diastereoselectivity Attainable in Aqueous, Organic, and Mixed Solvent Systems
  作者：Leo A. Paquette、Thomas M. Mitzel

  DOI：10.1021/ja953682c

  日期：1996.1.1

  The stereochemical course of indium-promoted allylations to alpha- and beta-oxy aldehydes has been investigated in solvents ranging from anhydrous THF to pure H2O. The free hydroxyl derivatives react with excellent diastereofacial control to give significantly heightened levels of syn-1,2-diols and anti-1,3-diols. Relative reactivities were determined in the alpha-series, and the hydroxy aldehyde proved to be the most reactive substrate. This reactivity ordering suggests that the selectivity stems from chelated intermediates. The rate acceleration observed in water can be heightened by initial acidification. Indeed, the indium-promoted allylation reaction mixtures become increasingly acidic on their own. Preliminary attention has been accorded to salt effects, and tetraethylammonium bromide was found to exhibit a positive synergistic effect on product distribution. Finally, mechanistic considerations are presented in order to allow for assessment of the status of these unprecedented developments at this stage of advancement of the field.