methyl (Z)-6-oxo-2-hexenoate | 99833-38-2

• 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: methyl (Z)-6-oxo-2-hexenoate
• 英文别名: methyl (Z)-6-oxohex-2-enoate
• CAS: 99833-38-2
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: VIPCJSCBXJTMQM-HYXAFXHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (Z)-6-oxo-2-hexenoate 在 二异丙氧基二氯化钛 、 碳酸氢钠 作用下， 以 hexanes 、 二氯甲烷 为溶剂， 反应 35.25h， 生成
  参考文献：
  名称：

  A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

  摘要：

  Despite over three decades of research into asymmetric phase-transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity:oriented approach wherein the tandem inter [4 + 2]/intra[3 + 2] cycloaddition of nitroalkenes serves as the key transformation. A two-part synthetic strategy comprised of (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way on the basis of the effective positive potential of the ammonium ion.

  DOI：

  10.1021/jo2005445
• 作为产物：
  描述：

  6-hydroxy-2-hexenoic acid ε-lactone 在 三氧化硫吡啶 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 0.33h， 生成 methyl (Z)-6-oxo-2-hexenoate
  参考文献：
  名称：

  A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

  摘要：

  Despite over three decades of research into asymmetric phase-transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity:oriented approach wherein the tandem inter [4 + 2]/intra[3 + 2] cycloaddition of nitroalkenes serves as the key transformation. A two-part synthetic strategy comprised of (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way on the basis of the effective positive potential of the ammonium ion.

  DOI：

  10.1021/jo2005445

文献信息

• Further observations on the rhodium (I)-catalysed tandem hydrosilylation-intramolecular aldol reaction
  作者：Marta Freirı́a、Andrew J Whitehead、Derek A Tocher、William B Motherwell

  DOI：10.1016/j.tet.2003.12.057

  日期：2004.3

  The rhodium (I) catalysed tandem hydrosilylation-intramolecular aldol reaction provides a simple strategy for construction of a range of usefully functionalised five-membered rings from readily prepared 6-oxo-2-hexenoates in good yield and with good to excellent stereoselectivity. A series of silanes and rhodium catalysts have been investigated. Stereoselectivity proved to be highly dependant on the

  铑（I）催化的串联氢化硅烷化-分子内醇醛缩合反应提供了一种简单的策略，可从容易制备的6-氧代-2-己烯酸酯以高收率和良好至极好的立体选择性构建一系列有用的官能化五元环。已经研究了一系列硅烷和铑催化剂。立体选择性被证明高度依赖于催化剂以及母体底物的取代模式。还已经评估了这种方法用于合成更大环尺寸的扩展。
• Selectivity in ozonolyses of cyclic 1,3-dienes
  作者：Zhaoyin Wang、Gury Zvlichovsky

  DOI：10.1016/s0040-4039(00)97901-2

  日期：——

  Selective cleavages of one double bond in various 1,3-cyclic dienes were studied. It was found that the regioselectivity of fragmentation of the resulting primary ozonides depends on the size of the rings.

  研究了在各种1,3-环二烯中一个双键的选择性裂解。已经发现，所产生的初级臭氧化物的片段化的区域选择性取决于环的大小。
• Tandem inter [4+2]/intra [3+2] nitroalkene cycloadditions. 4. Cycloadditions with (E)- and (Z)-1-propenyl ethers
  作者：Scott E. Denmark、C. B. W. Senanayake

  DOI：10.1021/jo00059a043

  日期：1993.3

  The tandem [4 + 2]/[3 + 2] cycloaddition of nitroalkene 1 was initiated efficiently by 1-propenyl ethers as the dienophile. Ethyl(E)-1-propenyl ether reacted highly selectively to give a single nitro so acetal cycloadduct 6. Hydrogenolysis of 6 afforded a single isomer of alpha-hydroxy lactam 8 wherein the newly installed methyl group occupied the beta-configuration. Similarly, ethyl(Z)-1-propenyl ether produced an anomeric mixture of cycloadducts 7a and 7b which afforded a single alpha-hydroxy lactam 9 upon hydrogenolysis. The methyl group in 9 occupied the alpha-orientation. The high and complementary selectivity for production of 8 and 9 was explained on the basis of an extreme endo preference for the ethoxy group of the 1-propenyl ether in the [4 + 2] cycloaddition.
• WANG, ZHAOYIN;ZVILICHOVSKY, GURY, TETRAHEDRON LETT., 31,(1990) N9, C. 5579-5582
  作者：WANG, ZHAOYIN、ZVILICHOVSKY, GURY

  DOI：——

  日期：——