1-Oxo-2-(4-oxobutyl)-cyclohexan | 142055-94-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Oxo-2-(4-oxobutyl)-cyclohexan
• 英文别名: Cyclohexanebutanal, 2-oxo-；4-(2-oxocyclohexyl)butanal
• CAS: 142055-94-5
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: BWIBXQPFJPLBDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  1-Oxo-2-(4-oxobutyl)-cyclohexan 在 六甲基二硅氮烷 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 12.17h， 生成 methyl (2E)-6-(2-trimethylsilyloxy-1-cyclohexenyl)-2-hexenoate
  参考文献：
  名称：

  在两种互补条件下通过串联分子内迈克尔-羟醛反应合成多环环丁烷衍生物：TBDMSOTf-Et3N 和 TMSI-(TMS)2NH

  摘要：

  通过串联的分子内迈克尔-羟醛反应序列，在 Et 3 N 存在下用 TBDMSOTf 或在 (TMS) 2 NH 存在下用 TMSI 处理在适当位置具有酮官能团的 α,β-不饱和酯，几种不同类型的环丁烷衍生物。这两种反应条件是互补的。三环[4.2.1.03-8]壬烷34和35、三环[5.1.1.0 3,8 ]壬烷40、三环[5.4.0.0 3,7 ]十一烷51、四环[5.4.0.0 3,7 .0 9,11 ]十一烷 45 和双环 [3.2.0] 庚烷 36、57 和 38，它们的结构部分或完全类似于端茚酸 A (1a)、B (1b) 和 C (2)、三羟基癸二烯(3)、lintenone (4)、italicene (3) 和 filifolone (6)，通过串联反应立体选择性地合成

  DOI：

  10.1021/ja00071a024
• 作为产物：
  描述：

  1,1'-联(环己烷)-1'-烯-2-胺 在 六甲基磷酰三胺 、 水 、 草酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 6.5h， 生成 1-Oxo-2-(4-oxobutyl)-cyclohexan
  参考文献：
  名称：

  在两种互补条件下通过串联分子内迈克尔-羟醛反应合成多环环丁烷衍生物：TBDMSOTf-Et3N 和 TMSI-(TMS)2NH

  摘要：

  通过串联的分子内迈克尔-羟醛反应序列，在 Et 3 N 存在下用 TBDMSOTf 或在 (TMS) 2 NH 存在下用 TMSI 处理在适当位置具有酮官能团的 α,β-不饱和酯，几种不同类型的环丁烷衍生物。这两种反应条件是互补的。三环[4.2.1.03-8]壬烷34和35、三环[5.1.1.0 3,8 ]壬烷40、三环[5.4.0.0 3,7 ]十一烷51、四环[5.4.0.0 3,7 .0 9,11 ]十一烷 45 和双环 [3.2.0] 庚烷 36、57 和 38，它们的结构部分或完全类似于端茚酸 A (1a)、B (1b) 和 C (2)、三羟基癸二烯(3)、lintenone (4)、italicene (3) 和 filifolone (6)，通过串联反应立体选择性地合成

  DOI：

  10.1021/ja00071a024

文献信息

• Preparation of Cyclic .ALPHA.-Hydroxy Ketones from .DELTA.- and .EPSILON.-Keto Acids Induced by the Generation of a Novel Acyl Anion Equivalent from the Carboxyl Group.
  作者：Hatsuo MAEDA、Haruka ASHIE、Toshihide MAKI、Hidenobu OHMORI

  DOI：10.1248/cpb.45.1729

  日期：——

  An improved method for the transformation of keto acids into cyclic α-hydroxy ketones, induced by the electrochemical generation of a novel acyl anion equivalent from the carboxy group, has been developed. Both five- and six-membered rings were constructed by constant-current electrolysis of δ- and ε-keto acids in the presence of Bu3P using an undivided cell equipped with a graphite anode and a Pt cathode. Attempts to prepare four- and seven-membered ring carbocycles were unsuccessful. The electrochemical reaction was found to be highly stereoselective when cyclization took place onto cyclopentanone and substituted cyclohexanone rings. Stereochemical aspects of the formation of bicyclic products, especially those having a bicyclo[4.3.0]skeleton, are discussed.

  开发了一种改进的方法，通过电化学生成从羧基衍生出的新型酰基阴离子等价物，诱导将酮酸转化为环状α-羟基酮。通过在配有石墨阳极和铂阴极的无隔膜电池中，在Bu3P存在下对δ-和ε-酮酸进行恒流电解，构建了五元和六元环。尝试制备四元和七元环碳环未能成功。当环化反应发生在环戊酮和取代环己酮环上时，发现该电化学反应具有高度立体选择性。讨论了双环产物形成的立体化学方面，特别是具有双环[4.3.0]骨架的产物。
• Efficient Platinum(II) Catalyzed Hydroformylation Reaction in Water: Unusual Product Distribution in Micellar Media
  作者：Marina Gottardo、Alessandro Scarso、Stefano Paganelli、Giorgio Strukul

  DOI：10.1002/adsc.201000341

  日期：2010.9.10

  Aldehydes are obtained with linear to branched ratios up to >99:1. With styrene derivatives also the corresponding benzaldehydes are formed. The catalyst can be separated by extraction of the organic products with hexane and recycled for at least four times with only a modest loss of activity and no effect on selectivity.

  在水性胶束介质中，在温和条件下，[P 2 Pt（H 2 O）2 ]（OTf）2型阳离子三氟甲磺酸铂络合物可以有效地进行各种末端和内部烯烃的加氢甲酰化。表面活性剂的使用对于确保催化剂和底物在水中的溶解是至关重要的，并且催化剂位于胶束的阴离子表面上。醛的线性与支化比率高达> 99：1。与苯乙烯衍生物也形成相应的苯甲醛。可以通过用己烷萃取有机产物来分离催化剂，并循环至少四次，只是活性损失不大，对选择性没有影响。
• A novel method for selective dioxolanation of ketones in the presence of aldehydes
  作者：Sunggak Kim、Yong Gil Kim、Deog-il Kim

  DOI：10.1016/s0040-4039(00)92243-3

  日期：1992.4

  Selective dioxolanation of ketones in the presence of aldehydes has been achieved by preferential in situ conversion of aldehydes into 1-silyloxysulfonium salts.

  通过将醛优先地原位转化成1-甲硅烷氧基s盐，已经实现了在醛存在下酮的选择性二恶唑酸化。
• Intramolecular Anodic Olefin Coupling Reactions: A New Approach to the Synthesis of Angularly Fused, Tricyclic Enones
  作者：Luzviminda V. Tinao-Wooldridge、Kevin D. Moeller、Christine M. Hudson

  DOI：10.1021/jo00088a019

  日期：1994.5

  A number of intramolecular anodic olefin coupling reactions have been examined in order to determine the feasibility of using a sequential electrochemical oxidation-aldol condensation approach for constructing polycyclic enones. Initially, substrates comprised of an aldehyde enol ether tethered to a ketone enol ether were examined. In a model study, it was shown that such a substrate could lead to a successful electrochemical oxidation-aldol condensation sequence. However, the difficulties associated with both the synthesis and the poor stability of the ketone enol ethers greatly reduced the potential utility of this approach. This problem was circumvented by taking advantage of the compatibility of allylsilane groups with the electrolysis reaction. In these examples, ozonolysis of the electrochemical cyclization product afforded the 1,4-dicarbonyl substrate needed for the aldol condensation. The use of the less reactive allylsilane group in the electrochemical reaction still allowed for the construction of quaternary carbons. Finally a pair of angularly fused, tricyclic enones were synthesized. The regiochemistry of the enone in the product could be controlled by the proper choice of the substrate for the electrolysis and manipulation of the resulting cyclized product.
• SmI₂-Promoted Intramolecular Asymmetric Pinacol-Type Ketone−<i>tert</i>-Butanesulfinyl Imine Reductive Coupling: Stereoselectivity and Mechanism
  作者：Bing Wang、Yong-Jun Wang

  DOI：10.1021/ol901296u

  日期：2009.8.6

  The asymmetric ketone-tert-butanesulfinyl (t-BS) imine pinacol-type reductive coupling promoted by SmI2 is described. Trans-1,2-vicinal amino alcohols were formed predominantly in excellent er and high dr. The stereochemical outcome provided evidence for a radical mechanism for SmI2-induced reductive couplings of t-BS imines.