(S)-2-ethyl-5-oxohexanal | 553638-75-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-2-ethyl-5-oxohexanal
• 英文别名: (2S)-2-Ethyl-5-oxohexanal
• CAS: 553638-75-8
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: QQYSXJCCOWNSSH-QMMMGPOBSA-N

物化性质

• 沸点：
  223.8±23.0 °C(Predicted)
• 密度：
  0.915±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,4S)-(+)-戊二醇 、 (S)-2-ethyl-5-oxohexanal 在 对甲苯磺酸 作用下， 以 氘代氯仿 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Synthesis of Optically Active 4-Substituted 2-Cyclohexenones

  摘要：

  Recently, Nicolaou and Baran independently synthesized optically active 4-substituted 2-cyclohexenones via an efficient LION-mediated intramolecular aldol condensation. Thus far, application of their cyclization approach has been limited to ketoaldehydes where the R-group is branched. It is demonstrated that the LiOH-mediated cyclization, when applied to substrates containing unbranched R-groups, results in significant erosion of optical purity. A mechanistic justification is provided, and a set of neutral, organocatalyzed conditions is identified that enables cyclization with little loss in optical purity.

  DOI：

  10.1021/ol301874x
• 作为产物：
  描述：

  丁烯酮 、 正丁醛 在 3,4-二羟基苯甲酸乙酯 、 (R)-3-benzyl-1-methyl-1,4-diazaspiro[4.4]nonan-2-one 作用下， 以72%的产率得到(S)-2-ethyl-5-oxohexanal
  参考文献：
  名称：

  Synthesis of Optically Active 4-Substituted 2-Cyclohexenones

  摘要：

  Recently, Nicolaou and Baran independently synthesized optically active 4-substituted 2-cyclohexenones via an efficient LION-mediated intramolecular aldol condensation. Thus far, application of their cyclization approach has been limited to ketoaldehydes where the R-group is branched. It is demonstrated that the LiOH-mediated cyclization, when applied to substrates containing unbranched R-groups, results in significant erosion of optical purity. A mechanistic justification is provided, and a set of neutral, organocatalyzed conditions is identified that enables cyclization with little loss in optical purity.

  DOI：

  10.1021/ol301874x

文献信息

• Direct Enantioselective Michael Addition of Aldehydes to Vinyl Ketones Catalyzed by Chiral Amines
  作者：Paolo Melchiorre、Karl Anker Jørgensen

  DOI：10.1021/jo026837p

  日期：2003.5.1

  enantioselectivities, using aldehydes and, e.g., methyl vinyl ketone as starting compounds. Taking into account that the chiral amine can activate the aldehyde and/or the enone, the mechanism for the reaction has been investigated. On the basis of intermediate synthesis, nonlinear effect, and theoretical investigations, the mechanism for the catalytic direct enantioselective Michael addition of aldehydes to vinyl ketones

  （S）-2- [双（3,5-二甲基苯基）甲基]吡咯烷和C（2）-对称（2S，5S）-2,5-二苯基吡咯烷等手性胺可以催化简单的对映选择性迈克尔加成反应醛到乙烯基酮。已经优化了该有机催化反应的条件，并且发现手性胺使用醛和例如甲基乙烯基酮作为起始化合物以良好的产率和对映选择性催化形成光学活性取代的5-酮醛。考虑到手性胺可以活化醛和/或烯酮，已经研究了反应机理。在中间综合，非线性效应和理论研究的基础上，
• A General Organocatalyst for Direct α-Functionalization of Aldehydes:  Stereoselective C−C, C−N, C−F, C−Br, and C−S Bond-Forming Reactions. Scope and Mechanistic Insights
  作者：Johan Franzén、Mauro Marigo、Doris Fielenbach、Tobias C. Wabnitz、Anne Kjærsgaard、Karl Anker Jørgensen

  DOI：10.1021/ja056120u

  日期：2005.12.1

  The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts.
• A Rapid ¹H NMR Assay for Enantiomeric Excess of α-Substituted Aldehydes
  作者：Yonggui Chi、Timothy J. Peelen、Samuel H. Gellman

  DOI：10.1021/ol051174u

  日期：2005.8.1

  [GRAPHICS]In situ derivatization of a variety of alpha-substituted aldehydes via reaction with chiral amines allows convenient and efficient determination of enantiomeric excess. H-1 NMR analysis of the imine diastereomer ratio can be conducted immediately after the aldehyde and amine have been mixed. The results correlate well with ee values determined by more traditional (and slower) methods. This approach may be broadly applicable to alpha-substituted aldehydes.
• Synthesis of Optically Active 4-Substituted 2-Cyclohexenones
  作者：Tania I. Houjeiry、Sarah L. Poe、D. Tyler McQuade

  DOI：10.1021/ol301874x

  日期：2012.9.7

  Recently, Nicolaou and Baran independently synthesized optically active 4-substituted 2-cyclohexenones via an efficient LION-mediated intramolecular aldol condensation. Thus far, application of their cyclization approach has been limited to ketoaldehydes where the R-group is branched. It is demonstrated that the LiOH-mediated cyclization, when applied to substrates containing unbranched R-groups, results in significant erosion of optical purity. A mechanistic justification is provided, and a set of neutral, organocatalyzed conditions is identified that enables cyclization with little loss in optical purity.