5-Carbomethoxyhex-5-ene-1-al | 135522-42-8

• 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: 5-Carbomethoxyhex-5-ene-1-al
• 英文别名: Methyl 2-methylidene-6-oxohexanoate
• CAS: 135522-42-8
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: KMAGGKISIVQMOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  5-Carbomethoxyhex-5-ene-1-al 在 盐酸羟胺 作用下， 以 水 、 乙腈 为溶剂， 反应 16.0h， 生成 (3aR,6aR)-Tetrahydro-cyclopenta[c]isoxazole-3a-carboxylic acid methyl ester
  参考文献：
  名称：

  X = Y-ZH系统为潜在的1,3-偶极子。第31部分：从肟中产生硝酮。1,2-原生质-分子内环加成序列的背景和范围。

  摘要：

  芳基和脂族肟中的1，2-原生质产生少量平衡浓度的相应NH硝酮。描述了涉及芳基和脂族肟的串联1,2-原生质-分子内环加成序列的实例，并讨论了有利或不利于该序列的空间和电子因素。用脂肪族肟进行氘标记的研究排除了烯羟胺参与NH硝酮的质子生成过程。

  DOI：

  10.1016/s0040-4020(01)86441-3
• 作为产物：
  描述：

  6,6-dimethoxy-2-methylene-hexanal 在 盐酸 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 potassium carbonate 、 溶剂黄146 作用下， 以 水 、 丙酮 、 叔丁醇 为溶剂， 反应 4.5h， 生成 5-Carbomethoxyhex-5-ene-1-al
  参考文献：
  名称：

  Highly Diastereoselective Synthesis of vicinal Quaternary and Tertiary Stereocenters Using the Iodo-aldol Cyclization

  摘要：

  The intramolecular iodo-aldol cyclization of alpha-substituted enoate aldehydes and ketones is described. Using prochiral starting materials, the reaction produces hetero- and carbocycles containing quaternary centers adjacent to secondary or tertiary centers. The reactions occur in good yields and are highly selective for the trans-products, having the hydroxyl and iodomethyl groups on opposite faces of the ring system.

  DOI：

  10.1021/ol070482k

文献信息

• X = Y - ZH systems as potential 1,3-dipoles part 35. Generation of nitrones from oximes. Class 3 processes. Tandem intramolecular michael addition (1,3-azaprotio cyclotransfer) - intermolecular 1,3-dipolar cycloaddition reactions.
  作者：Ronald Grigg、Jasothara Markandu、Trevor Perrior、Sivagnanasundram Surendrakumar、William J. Warnock

  DOI：10.1016/s0040-4020(01)89883-5

  日期：1992.1

  Aldoximes and ketoximes possessing gamma- or delta-alkenyl substituents undergo thermal conversion to 5- and 6- membered cyclic nitrones via a 1,3-azaprotio cyclotransfer, a 2n + 2-sigma + 2-pi concerted process, rather than a Michael addition. The reactions can be performed as a tandem nitrone formation-cycloaddition sequence or, if required, the intermediate nitrones can be isolated. The cycloadditions usually proceed via an exo-transition state and show both regio- and diastereofacial-specificity. Preliminary attempts at chiral induction via a menthyl auxiliary are reported.
• Highly Diastereoselective Synthesis of <i>vicinal</i> Quaternary and Tertiary Stereocenters Using the Iodo-aldol Cyclization
  作者：Frederic Douelle、Amy S. Capes、Michael F. Greaney

  DOI：10.1021/ol070482k

  日期：2007.5.1

  The intramolecular iodo-aldol cyclization of alpha-substituted enoate aldehydes and ketones is described. Using prochiral starting materials, the reaction produces hetero- and carbocycles containing quaternary centers adjacent to secondary or tertiary centers. The reactions occur in good yields and are highly selective for the trans-products, having the hydroxyl and iodomethyl groups on opposite faces of the ring system.
• X=Y-ZH systems as potential 1,3-dipoles. Part 31. Generation of nitrones from oximes. Background and scope of the tandem 1,2-prototropy-intramolecular cycloaddition sequence.
  作者：Ronald Grigg、Frances Heaney、Jasothara Markandu、Sivagnanasundram Surendrakumar、Thornton-Pett Mark、Warnock J. William

  DOI：10.1016/s0040-4020(01)86441-3

  日期：1991.1

  and electronic factors that favour or disfavour such a sequence are discussed. Deuterium labelling studies with an aliphatic oxime rule out the involvement of an enehydroxylamine in the prototropic generation of the NH nitrone.

  芳基和脂族肟中的1，2-原生质产生少量平衡浓度的相应NH硝酮。描述了涉及芳基和脂族肟的串联1,2-原生质-分子内环加成序列的实例，并讨论了有利或不利于该序列的空间和电子因素。用脂肪族肟进行氘标记的研究排除了烯羟胺参与NH硝酮的质子生成过程。