2-acetyl-hept-6-ynoate de tertiobutyle | 146445-32-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-acetyl-hept-6-ynoate de tertiobutyle
• 英文别名: tert-butyl 2-acetylhept-6-ynoate；Tert-butyl 2-acetylhept-6-ynoate
• CAS: 146445-32-1
• 化学式: C₁₃H₂₀O₃
• 分子量: 224.3
• InChiKey: VOQBKBLFBPGUCF-UHFFFAOYSA-N

物化性质

• 沸点：
  311.7±32.0 °C(Predicted)
• 密度：
  0.984±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  2-acetyl-hept-6-ynoate de tertiobutyle 在 Pd(dppe) potassium tert-butylate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 8.0h， 生成 (6ci,9ci)-2-甲基-1-环戊烯-1-羧酸
  参考文献：
  名称：

  Formation de derives cyclopentaniques assistee par une espece hydrure de palladium : Aspects synthetiques et mecanisme

  摘要：

  In the presence of a palladium(0) complex and potassium t-butoxide, the acetylenic compounds 2 bearing in delta a nucleophilic functionality are smoothly transformed with excellent yields, either into 2,2-difunctionalized methylene cyclopentanes or into monofunctionalized 2-methylcyclopentenes. Each of these compounds can be specifically obtained depending on the choice of the experimental conditions.A set of diverse reactions involving mainly potassium hydride as the base showed clearly that HPdOtBu is not the active catalytic species which is mainly a sigma-ethynylpalladium hydride formed by the metal insertion in the acetylenic carbon hydrogen bond.

  DOI：

  10.1016/s0040-4020(01)89040-2
• 作为产物：
  描述：

  乙酰乙酸叔丁酯 、 5-碘-1-戊炔 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以83%的产率得到2-acetyl-hept-6-ynoate de tertiobutyle
  参考文献：
  名称：

  Formation de derives cyclopentaniques assistee par une espece hydrure de palladium : Aspects synthetiques et mecanisme

  摘要：

  In the presence of a palladium(0) complex and potassium t-butoxide, the acetylenic compounds 2 bearing in delta a nucleophilic functionality are smoothly transformed with excellent yields, either into 2,2-difunctionalized methylene cyclopentanes or into monofunctionalized 2-methylcyclopentenes. Each of these compounds can be specifically obtained depending on the choice of the experimental conditions.A set of diverse reactions involving mainly potassium hydride as the base showed clearly that HPdOtBu is not the active catalytic species which is mainly a sigma-ethynylpalladium hydride formed by the metal insertion in the acetylenic carbon hydrogen bond.

  DOI：

  10.1016/s0040-4020(01)89040-2

文献信息

• Mild and Functional Group Tolerant Method for Tandem Palladium-Catalyzed Carbocyclization-Coupling of ε-Acetylenic β-Ketoesters with Aryl Bromides and Chlorides
  作者：Wojciech Chaładaj、Sylwester Domański

  DOI：10.1002/adsc.201600175

  日期：2016.6.2

  report a new protocol for the annulative difunctionalization of acetylenes via tandem carbocyclization–coupling of ε‐acetylenic β‐ketoesters with aryl and heteroaryl bromides and chlorides catalyzed by the palladium species derived from an air‐ and moisture‐stable palladacyclic precatalyst. In the tandem process, the palladium complex combines appropriate carbophilic Lewis acidity and redox activity to catalyze

  我们报告了一种通过串联碳环化来实现乙炔的双官能双官能化的新方案，即通过空气和水分稳定的四环前催化剂衍生的钯物种催化的ε-炔属β-酮酸酯与芳基和杂芳基溴化物和氯化物的偶联。在串联过程中，钯配合物结合了适当的嗜碳路易斯酸度和氧化还原活性，以催化两个机理上截然不同的反应-亲核性将烯酸酯加成至未活化的炔烃，然后进行CC偶联。
• Asymmetric Catalysis with Iron–Salen Complexes
  作者：James White、Subrata Shaw

  DOI：10.1055/s-0035-1562103

  日期：——

  β-dicarbonyl compounds. The use of these chiral iron–salen complexes as catalysts provides a new method for conducting these three important reactions under environmentally sustainable conditions. Iron(III)–salen complexes based on a chiral cis-2,5-diaminobicyclo[2.2.2]octane scaffold are used as catalysts for a variety of stereo­selective reactions. High enantio- and diastereoselectivities can be achieved with

  摘要 基于手性顺式-2,5-二氨基双环[2.2.2]辛烷骨架的铁（III）-salen配合物被用作各种立体选择性反应的催化剂。这些催化剂在磺胺-迈克尔共轭物添加到无环α，β-不饱和酮中，硫醇的区域选择性δ加成到无环α，β，γ，δ-不饱和酮中以及在Conia-中可以实现高对映体和非对映选择性。炔基取代的β-二羰基化合物的烯碳环化。这些手性铁-salen配合物的使用为在环境可持续条件下进行这三个重要反应提供了一种新方法。 基于手性顺式-2,5-二氨基双环[2.2.2]辛烷骨架的铁（III）-salen配合物被用作各种立体选择性反应的催化剂。这些催化剂在磺胺-迈克尔共轭物添加到无环α，β-不饱和酮中，硫醇的区域选择性δ加成到无环α，β，γ，δ-不饱和酮中以及在Conia-中可以实现高对映体和非对映选择性。炔基取代的β-二羰基化合物的烯碳环化。这些手性铁-salen配合物的使用为在环境可持续条件下进行这三个重要反应提供了一种新方法。
• Development of an enantioselective amine–silver co-catalyzed Conia-ene reaction
  作者：M. Blümel、D. Hack、L. Ronkartz、C. Vermeeren、D. Enders

  DOI：10.1039/c7cc01807j

  日期：——

  The development of a novel cooperative catalytic system for an amine–silver co-catalyzed Conia-ene reaction of alkyne-tethered C–H-acidic compounds is reported.

  报道了一种新型的合作催化系统，用于氨基-银共催化的炔基-锚定C-H酸性化合物的Conia-ene反应。
• Iron(III)-Catalyzed Conia–Ene Cyclization of 2-Alkynic 1,3-Dicarbonyl Compounds
  作者：Li Yan Chan、Sunggak Kim、Youngchul Park、Phil Ho Lee

  DOI：10.1021/jo300957q

  日期：2012.6.15

  A cheap, simple, and effective FeCl3-catalyzed Conia–ene cyclization of 2-alkynic 1,3-dicarbonyl compounds was stereospecific to afford alkylidenecyclopentanes in (E)-isomers via the 5-exo-dig pathway. The 5-endo-dig and 6-exo-dig cyclizations were also possible, depending on the structure of the substrates.

  廉价，简单，有效的FeCl 3催化的2-炔烃1,3-二羰基化合物的Conia-ene环化具有立体特异性，可以通过5 -exo-dig途径得到（E）异构体中的亚烷基环戊烷。根据底物的结构，也可以进行5 -endo-dig和6 -exo-dig环化。
• Bulky Thioureas as New Ligands for Gold(I)-Catalyzed Cyclization of Acetylenic 1,3-Dicarbonyl Compounds
  作者：Dan Yang、Jie-Hui Pan、Min Yang、Qiang Gao、Nian-Yong Zhu

  DOI：10.1055/s-2007-983804

  日期：2007.8

  N′-disubstituted cyclic thioureas as ligands for gold(I) catalysis. X-ray crystal structures of the thiourea-gold(I) complexes presented important information about the nature of the complexation. These complexes were found to be active catalysts for the cyclization of 1,3-dicarbonyl compounds with alkynes (Conia-ene reaction). Various acetylenic 1,3-dicarbonyl compounds underwent cycloisomerization to give mono-

  我们说明了第一次使用庞大的 N,N'-二取代环状硫脲作为金 (I) 催化的配体。硫脲-金 (I) 配合物的 X 射线晶体结构提供了有关配合物性质的重要信息。发现这些配合物是 1,3-二羰基化合物与炔烃的环化反应（Conia-ene 反应）的活性催化剂。在 1 mol% 的硫脲-氯化金 (I) 络合物和三氟甲磺酸银存在下，各种炔属 1,3-二羰基化合物经过环化异构化得到单环和双环烯属环戊烷。