2-((2S,3S)-2,3-Dihydroxy-pentyl)-3-methyl-cyclopent-2-enone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-((2S,3S)-2,3-Dihydroxy-pentyl)-3-methyl-cyclopent-2-enone
• 英文别名: 2-[(2S,3S)-2,3-dihydroxypentyl]-3-methylcyclopent-2-en-1-one
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: FURAJJFYNXGVLJ-ONGXEEELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-((2S,3S)-2,3-Dihydroxy-pentyl)-3-methyl-cyclopent-2-enone 在 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 乙酸酐 为溶剂， 反应 6.0h， 生成 trans-jasmone
  参考文献：
  名称：

  通过 2-甲氧基-1,3-二氧戊环衍生物将邻二醇温和地立体特异性地转化为烯烃

  摘要：

  报道了一种通过相应的 2-甲氧基-1,3-二氧戊环从邻二醇立体定向合成烯烃的有效且实用的方法。

  DOI：

  10.1246/cl.1986.879
• 作为产物：
  描述：

  茉莉酮 在 N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamineiron(II) bis(triflate) 、 双氧水 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以80%的产率得到2-((2S,3S)-2,3-Dihydroxy-pentyl)-3-methyl-cyclopent-2-enone
  参考文献：
  名称：

  Oxidation of alkenes with non-heme iron complexes: suitability as an organic synthetic method

  摘要：

  In the course of a preliminary study to determine the preparative value and the synthetic applications of the non-heme iron(II) complexes Fe(bpmen)(OTf)(2) and Fe(tpa)(OTf)(2), in particular the oxidation of alkenes by using hydrogen peroxide as the terminal oxidant, we have found significant differences in catalyst behavior. After several attempts it was clear that the preparative relevance of the oxidation processes was linked to the concentration of the catalyst and optimal results were obtained when the concentration value was 5 mol %. At that concentration, the Fe(bpmen)(OTf)(2) catalyst mostly gave rise to mixtures of the epoxide and the trans-dihydroxylation products formed by water-assisted hydrolytic cleavage of the epoxides. Furthermore, the use of the tripodal ligand tpa led to cis dihydroxylation products. When deactivated olefins were used as substrates for the oxidation reaction, the cis-diols were obtained exclusively, although with modest conversions, regardless of the catalyst used. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.10.037

文献信息

• Mechanistically Driven Development of an Iron Catalyst for Selective <i>Syn</i>-Dihydroxylation of Alkenes with Aqueous Hydrogen Peroxide
  作者：Margarida Borrell、Miquel Costas

  DOI：10.1021/jacs.7b07909

  日期：2017.9.13

  to be resolved in the design of iron catalysts for olefin syn-dihydroxylation with potential utility in organic synthesis. Toward this end, in this work a novel catalyst bearing a sterically encumbered tetradentate ligand based in the tpa (tpa = tris(2-methylpyridyl)amine) scaffold, [FeII(CF3SO3)2(5-tips3tpa)], 1 has been designed. The steric demand of the ligand was envisioned as a key element to support

  产物释放是在 Rieske 加氧酶发生的芳烃合成二羟基化反应中的速率决定步骤，被认为是设计用于烯烃合成二羟基化的铁催化剂中需要解决的难题，在有机合成中具有潜在的应用价值。为此，在这项工作中，设计了一种基于 tpa（tpa = 三（2-甲基吡啶基）胺）支架 [FeII(CF3SO3)2(5-tips3tpa)], 1 的新型催化剂. 配体的空间需求被认为是通过隔离金属中心、防止双分子分解路径和促进产物释放来支持高催化活性的关键元素。与有助于螯合产品的路易斯酸协同组合，在温和的实验条件下，使用稍微过量（1.5 当量）的过氧化氢水溶液，在很短的反应时间内，从广泛范围的烯烃的氧化中，1 提供了良好到极好的二醇产物产率（高达 97% 的分离产率）。显示了二烯烃的可预测位点选择性顺式二羟基化。配体的受阻性质也提供了一种独特的工具，该工具已与同位素分析结合使用，以确定活性物质的性质和 H2O2 的活化机制。此外，1
• Fe(PyTACN)-Catalyzed<i>cis</i>-Dihydroxylation of Olefins with Hydrogen Peroxide
  作者：Irene Prat、David Font、Anna Company、Kathrin Junge、Xavi Ribas、Matthias Beller、Miquel Costas

  DOI：10.1002/adsc.201200938

  日期：2013.3.25

  catalysts for efficient and selective alkene oxidation (epoxidation and cis‐dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(Me,Me,HPyTACN)(CF3SO3)2] (7), was identified as the most efficient and selective cis‐dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the

  通式为[Fe（II）（R，Y，X PyTACN）（CF 3 SO 3）2 ]的铁络合物家族，其中R，Y，X PyTACN = 1‐ [2′‐（4‐Y‐6 -[X-吡啶基）甲基] -4,7-二烷基-1,4,7-三氮杂环壬烷，X和Y分别表示吡啶的4和6位上的基团，R表示在N-处的烷基取代基三氮杂双环壬烷环的4和N-7被证明是使用过氧化氢作为氧化剂进行有效且选择性的烯烃氧化（环氧化和顺式-二羟基化）的催化剂。络合物[Fe（II）（Me，Me，H PyTACN）（CF 3 SO 3）2 ]（7）被认为是该家族中最有效和选择性最强的顺式-二羟基化催化剂。7的高活性使烯烃的氧化在室温下以及在不大量使用烯烃而仅是限制性试剂的条件下迅速进行（30分钟）。在3％（摩尔）的存在下7，2当量。H 2 O 2作为氧化剂，当量为15当量。在乙腈溶液中，水被烯烃顺式-二羟基化，其收率可能对于合成目的是令人感兴趣的。竞
• A MILD AND STEREOSPECIFIC CONVERSION OF VICINAL DIOLS INTO OLEFINS VIA 2-METHOXY-1,3-DIOXOLANE DERIVATIVES
  作者：Masayoshi Ando、Hiroshi Ohhara、Kahei Takase

  DOI：10.1246/cl.1986.879

  日期：1986.6.5

  An efficient and practical method for the stereospecific synthesis of olefins from vicinal diols via the corresponding 2-methoxy-1,3-dioxolanes is reported.

  报道了一种通过相应的 2-甲氧基-1,3-二氧戊环从邻二醇立体定向合成烯烃的有效且实用的方法。
• Oxidation of alkenes with non-heme iron complexes: suitability as an organic synthetic method
  作者：David Clemente-Tejeda、Francisco A. Bermejo

  DOI：10.1016/j.tet.2014.10.037

  日期：2014.12

  In the course of a preliminary study to determine the preparative value and the synthetic applications of the non-heme iron(II) complexes Fe(bpmen)(OTf)(2) and Fe(tpa)(OTf)(2), in particular the oxidation of alkenes by using hydrogen peroxide as the terminal oxidant, we have found significant differences in catalyst behavior. After several attempts it was clear that the preparative relevance of the oxidation processes was linked to the concentration of the catalyst and optimal results were obtained when the concentration value was 5 mol %. At that concentration, the Fe(bpmen)(OTf)(2) catalyst mostly gave rise to mixtures of the epoxide and the trans-dihydroxylation products formed by water-assisted hydrolytic cleavage of the epoxides. Furthermore, the use of the tripodal ligand tpa led to cis dihydroxylation products. When deactivated olefins were used as substrates for the oxidation reaction, the cis-diols were obtained exclusively, although with modest conversions, regardless of the catalyst used. (C) 2014 Elsevier Ltd. All rights reserved.