2-bromohept-6-enoic acid | 269407-45-6

• 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: 2-bromohept-6-enoic acid
• 英文别名: 2-Bromohept-6-enoic acid
• CAS: 269407-45-6
• 化学式: C₇H₁₁BrO₂
• 分子量: 207.067
• InChiKey: VWTUPBYRRSLSCC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-bromohept-6-enoic acid 在 氯化亚砜 、 sodium hydroxide 作用下， 反应 21.17h， 生成 2-methoxyhept-6-enoic acid
  参考文献：
  名称：

  自由基复兴时期的 宝藏–杂己基自由基动力学数据† ‡

  摘要：

  已针对一系列具有不同电子和空间需求的取代己烯基确定了速率常数数据和Arrhenius参数。相对于捐赠基团（OMe ），直接连接至自由基中心的吸电子基团（CF 3，CO 2 Et）缓慢促进5- exo闭环（25°时k cis + k trans〜2.1 ×10 5 s -1） ；在25°时为1.6×10 5 s -1）。如预期的那样，对空间要求较高的组（叔-Bu ）减慢环化过程（1×10 5 s -1）。这些观察结果与5 - exo闭环的活化能的细微变化是一致的。有趣的是，溶剂的性质似乎对该化学有重大影响，随着溶剂极性的增加，顺式/反式立体选择性有时会提高。除了包含CF 3（吸电子）基团的系统显示出环化/捕获速率常数（k c / k H）增加外，k c / k H普遍下降。记录随着溶剂极性增加的比率；据推测，这些变化主要是由于所用各种溶剂中k H的变化引起的。

  DOI：

  10.1039/c0ob00708k
• 作为产物：
  描述：

  6-氧代己酸甲酯 在 氢氧化钾 、 四溴化碳 、 lithium diisopropyl amide 作用下， 以 甲醇 为溶剂， 生成 2-bromohept-6-enoic acid
  参考文献：
  名称：

  A short synthesis of (±)-alloyohimbane via a thioisomünchnone based intramolecular dipolar-cycloaddition reaction

  摘要：

  Thioisomunchnone dipoles were generated by the reaction of bromoalkenoyl chlorides with thioamides. The intramolecular dipolar-cycloaddition reaction was used for a short synthesis of the yohimbanoid alkaloid (+/-)-alloyohimbane. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00901-0

文献信息

• Radical-clock α-halo-esters as mechanistic probes for bisphosphine iron-catalyzed cross-coupling reactions
  作者：Lei Liu、Wes Lee、Jun Zhou、Surjo Bandyopadhyay、Osvaldo Gutierrez

  DOI：10.1016/j.tet.2018.11.043

  日期：2019.1

  C(sp2)-C(sp3) cross-coupling reactions has been studied via the synthesis of novel radical-clock α-halo-esters and quantum mechanical calculations. These results provide insights into the role of the substrate (halogen and substituents) in competing in-cage and out-of-cage arylation pathways and provide a basis for the future rational design of novel tandem cyclization-arylation reactions using bisphosphine-iron

  通过合成新颖的自由基钟α-卤代酯和量子力学计算，研究了手性双膦铁催化的C（sp 2）-C（sp 3）交叉偶联反应的机理。这些结果为洞察底物（卤素和取代基）在竞争笼内和笼外芳构化途径中的作用提供了见识，并为未来以双膦-铁为催化剂的新型串联环化芳构化反应的合理设计提供了基础。 。
• Visible-Light-Driven Aryl Migration and Cyclization of α-Azido Amides
  作者：Siyu Liang、Kaijie Wei、Yajun Lin、Tuming Liu、Dian Wei、Bing Han、Wei Yu

  DOI：10.1021/acs.orglett.1c01120

  日期：2021.6.18

  i-Pr2NEt as the reducing agent, N-aryl α-azido tertiary amides were first converted to the corresponding aminyl radicals through reduction of the azido group; the aminyl radicals then underwent N-to-N aryl migration to give α-anilinyl-functionalized amides. α-Azido secondary amides, on the other hand, reacted with the solvent ethanol and i-Pr2NEt to afford the imidazolinone products.

  本文报道了 α-叠氮酰胺的两种新的可见光促进自由基反应。通过以i- Pr 2 NEt为还原剂催化[Ir(ppy) 2 (dtbbpy)]PF 6，N-芳基α-叠氮叔酰胺首先通过叠氮基的还原转化为相应的胺基；然后氨基自由基经历 N 到 N 芳基迁移，得到 α-苯胺基官能化的酰胺。另一方面，α-叠氮仲酰胺与溶剂乙醇和i- Pr 2 NEt 反应得到咪唑啉酮产物。
• Stereocontrol in Radical Cyclization: Change in Rate-Determining Step
  作者：Siddiki S. M. A. Hakim、Takashi Sugimura

  DOI：10.1021/ol101370x

  日期：2010.8.20

  substituent, while the selectivity becomes high to give a single stereoisomer (>99% pure) when the substituent is an aryl group. The difference in the selectivity is attributable to the change in the rate-determining step from the conformational process to the cyclization.

  带有手性2,4-戊二醇系链的酯的α-碳自由基的分子内环化显示，当自由基碳原子具有烷基取代基时，立体选择性低，而当取代基具有较高的选择性时，则可以生成单一的立体异构体（纯度> 99％）是芳基。选择性的差异可归因于从构象过程到环化过程的速率确定步骤的变化。
• A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems
  作者：Albert Padwa、L. Scott Beall、Todd M. Heidelbaugh、Bing Liu、Scott M. Sheehan

  DOI：10.1021/jo991742h

  日期：2000.5.1

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.
• Novel peroxide monomer and a polymer therefrom
  申请人：Nippon Paint Co., Ltd.

  公开号：EP0294237B1

  公开（公告）日：1992-11-25