methyl-2 (oxo propyl-2)-2 dioxolanne-1,3 | 79012-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-2 (oxo propyl-2)-2 dioxolanne-1,3
• 英文别名: 2-methyl-3-oxobutanal 3-ethylene ketal；2-(2-Methyl-1,3-dioxolan-2-yl)propanal
• CAS: 79012-35-4
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: ZNSHJLNTTCEYQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl-2 (oxo propyl-2)-2 dioxolanne-1,3 在 sodium hydroxide 、 三氟化硼乙醚 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 、 paraffin 为溶剂， 反应 4.5h， 生成 4,5-二甲基-2-呋喃甲酸
  参考文献：
  名称：

  Klein, Larry L., Synthetic Communications, 1986, vol. 16, # 4, p. 431 - 436

  摘要：

  DOI：
• 作为产物：
  描述：

  ethyl 3,3-ethylenedioxy-2-methylbutanoate 在 lithium aluminium tetrahydride 、 重铬酸吡啶 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 methyl-2 (oxo propyl-2)-2 dioxolanne-1,3
  参考文献：
  名称：

  Reactivite des衍生出decyclopropylidene-3 propyle-I：合成d'alcoolsβ-cyclopropylideniques

  摘要：

  通过以下顺序合成了一系列的β-环亚丙基醇：（i）在环亚丙基三苯基苯基膦与适当的单保护的1，3-二羰基化合物之间的维蒂希缩合；（ii）缩醛的平滑水解（在必要的反缩醛化步骤之后），从而形成缩酮；（iii）LAH还原醛和酮（分别产生伯醇和仲醇）或用甲基锂处理酮（产生叔醇）。

  DOI：

  10.1016/s0040-4020(01)98934-3

文献信息

• Reactivite des derives de cyclopropylidene-3 propyle-I
  作者：M. Bertrand、G. Leandri、A. Meou

  DOI：10.1016/s0040-4020(01)98934-3

  日期：1981.1

  β-cyclopropylidenic alcohols has been synthesized through the following sequence: (i) Wittig condensation between cyclopropylidenetriphenylphosphorane with appropriate monoprotected 1,3-dicarbonyl compounds; (ii) smooth hydrolysis of acetals (after a necessary transacetalization step) and ketals thus formed; (iii) LAH reduction of aldehydes and ketones (yielding primary and secondary alcohols respectively)

  通过以下顺序合成了一系列的β-环亚丙基醇：（i）在环亚丙基三苯基苯基膦与适当的单保护的1，3-二羰基化合物之间的维蒂希缩合；（ii）缩醛的平滑水解（在必要的反缩醛化步骤之后），从而形成缩酮；（iii）LAH还原醛和酮（分别产生伯醇和仲醇）或用甲基锂处理酮（产生叔醇）。
• Synthesis and Biological Evaluation of Subglutinol Analogs for Immunomodulatory Agents
  作者：Hyeri Park、Laura S. Christian、Mi Jung Kim、Qi-Jing Li、Jiyong Hong

  DOI：10.1021/acs.jmedchem.9b01579

  日期：2020.1.9

  requirements of subglutinols for immunomodulatory activity and to provide guiding principles on future therapeutic development, we prepared and evaluated several subglutinol analogs for their immunomodulatory activities. Our efforts identified a subglutinol analog with reduced structural complexity as a potential lead compound for future autoimmune drug development. Our study will provide an important

  自身免疫性疾病是与高发病率和高死亡率相关的慢性炎症性疾病。在过去的几十年中，自身免疫性疾病的治疗选择有所增加，但是由于高毒性和缺乏选择性，它们的临床疗效普遍受到限制。因此，必须努力确定通过新机制有效规避现有副作用的新的免疫调节剂。为了定义亚谷蛋白的免疫调节活性的结构要求，并为将来的治疗发展提供指导原则，我们准备并评估了几种亚谷蛋白类似物的免疫调节活性。我们的努力确定了结构复杂性降低的谷胱甘肽类似物作为未来自身免疫药物开发的潜在先导化合物。
• An Efficient Stereoselective Total Synthesis of dl-Sesquicillin, a Glucocorticoid Antagonist
  作者：Fei Zhang、Samuel J. Danishefsky

  DOI：10.1002/1521-3773(20020415)41:8<1434::aid-anie1434>3.0.co;2-a

  日期：2002.4.15
• Aldol Reactions with Kinetic Resolution: Scope and Limitations of Ketal- and Dithioketal-Protected β-Ketoaldehydes
  作者：Dale E. Ward、Alieh Kazemeini

  DOI：10.1021/jo302142v

  日期：2012.12.7

  The multiplicativity rule suggests that aldol coupling chiral reactants will proceed with substantial mutual kinetic enantioselection (MKE) (racemic reactants) or via a highly enantioselective kinetic resolution (KR) (one enantiopure reactant) if the relative topicity is highly selective and the ketone enolate and aldehyde each have high diastereoface selectivity. The scope and limitations of that paradigm were explored by determining the stereoselectivities of aldol reactions ketone 1a (known to give 3,5-trans aldol adducts with high selectivity) with a series of ketal- and dithioketal-protected beta-ketoaldehydes (+/-)-5 (predicted to have high Felkin diastereoface selectivity). Using racemic reactants, all reactions of the (c-Hex)(2)B enolates (highly anti-selective relative topicity) were remarkably selective and gave the 3,5-trans-3,1 ''-anti-1 '',2 ''-syn adduct, one of eight possible diastereomers, via a diastereomers, via a diastereoselective (dr > 20) preferential reaction (MKE > 17) of like reactant enantiomers [i.e., (3R)-1a + (R)-5 and (3S)-1a + (S)-5]. Reactions of the corresponding Ti(IV) "ate" enolates (anticipated syn-selective relative topicity) were much less selective, and only those of MOM-protected 1a with dithiolane-protected (+/-)-5 (i.e., X = S, n = 1) gave high selectivity in favor of the 3,5-trans-3,1 ''-syn-1 '', 2 ''-syn adduct via a diastereoselective (dr > 20) preferential reaction (MKE >= 6) of unlike reactant enantiomers [i.e., (3R)-1a (R = MOM) with (+/-)-5c (R-2 = Me, X = S, n = 1) occured withKR to give the corresponding enantiopure adducrs with the expected stereoselectivity. The adducts have applications in polyproionate synthesis.
• Divergent Synthesis of Pyrone Diterpenes via Radical Cross Coupling
  作者：Rohan R. Merchant、Kevin M. Oberg、Yutong Lin、Alexander J. E. Novak、Jakob Felding、Phil S. Baran

  DOI：10.1021/jacs.8b04891

  日期：2018.6.20

  A divergent strategy for assembling pyrone diterpenes is presented. Capitalizing on the unique stereo-and chemoselectivity features of radical-based chemistry, the core decalin of these structures is efficiently forged using an electrochemically assisted oxidative radical polycyclization while key peripheral substituents are appended using decarboxylative radical cross couplings. In this way, access to four natural products (subglutinols A/B, higginsianin A, and sesquicillin A) is achieved in a concise and stereocontrolled fashion that is modular and amenable to future medicinal chemistry explorations.