2-(4-戊炔基)-1-环戊酮 | 130741-30-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-(4-戊炔基)-1-环戊酮
• 英文名称: 2-(4-pentynyl)-1-cyclopentanone
• 英文别名: 2-(pent-4-ynyl)cyclopentanone；2-(4-pentynyl)cyclopentanone；2-pent-4-ynylcyclopentanone；(Pentin-4'-yl)-2-cyclopentanon-1；2-Pent-4-ynylcyclopentan-1-one
• CAS: 130741-30-9；42797-75-1
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: AMRPCZIAGNDBDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(4-戊炔基)-1-环戊酮 在 sodium methylate 、 六正丁基二锡 、 sodium hydride 、 二甲基亚砜 、 间氯过氧苯甲酸 、 六甲基二硅氮烷 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 44.84h， 生成 2,3-dimethoxy-6-methylenespiro[4.4]non-2-en-1-one
  参考文献：
  名称：

  Total Synthesis of Dimethyl Glolosiphone Aviaα-Carbonyl Radical Spiro-Cyclization

  摘要：

  AbstractA general approach toward spiro[4.4]nonane structure based on the α‐carbonyl radical cyclization has been developed. Efficient total synthesis of dimethyl gloiosiphone A (2) was achieved. Thus, alkylation of the anion of dimethylhydrazone of cyclopentanone with 5‐iodopent‐1‐yne followed by hydrolysis gave ketone 4. Iodination of 4 via its TMS‐enol ether yielded iodo ketone 7. Radical spiro‐cyclization of 7 gave spiro ketone 10. Iodination of 10 afford iodo spiro ketone 23. Oxidation and iodination of 23 gave compound 24. Methylation of 24 furnished methoxy iodo enone 25. Substitution of iodide in 25 with methoxide produced dimethoxy enone 26. Allylic oxidation of 26 gave diketone 27. Treatment of 27 with OsO4 and N‐methylmorpholine N‐oxide gave dihydroxy ketone 28. Methylation of the primary alcohol group in 28 afforded dimethyl gloiosiphone A (2).

  DOI：

  10.1002/jccs.199900064
• 作为产物：
  描述：

  5-碘-1-戊炔 在 sodium hydride 、 lithium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 2-(4-戊炔基)-1-环戊酮
  参考文献：
  名称：

  硫酚介导的1,5-氢原子抽象：轻松获得单环和双环化合物

  摘要：

  描述了硫代苯酚介导的炔烃环化方法。反应级联反应涉及在分子间将苯基噻吩基分子间加成到末端三键上，从而产生烯基基团，然后进行1，5-氢原子转移和5- exo- trig自由基环化。这种非常有效的无锡程序使人们可以从容易获得的前体制备高度官能化的环戊烷衍生物以及稠合的双环和螺环化合物。在该环化过程中，将苯硫基部分掺入最终的环化产物中。这种功能化对于产品的进一步转化特别有吸引力。

  DOI：

  10.1002/adsc.200505211

文献信息

• In situ intramolecular catalytic 1,2-addition of allenoates to cyclic ketones towards polycyclic allenoates
  作者：Clément F. Heinrich、Michel Miesch、Laurence Miesch

  DOI：10.1039/c4ob02451f

  日期：——

  Sequential deprotonation, isomerization of 3-alkynoates and subsequent 1,2-addition led to bicyclic allenoate in the presence of a catalytic amount of Cs2CO3. Cyclization proceeds in a totally stereoselective manner in the case of the two-carbon linker chain. A one-pot reaction starting from alkynyl ketones afforded tricyclic fused ring systems with good yields.

  在催化量的Cs 2 CO 3存在下，连续的去质子化，3-链烷酸酯的异构化以及随后的1,2-加成导致双环烯丙酸酯。在二碳连接子链的情况下，环化以完全立体选择性的方式进行。从炔基酮开始的一锅反应得到具有良好收率的三环稠合环系统。
• Intramolecular reductive ketone–alkynoate coupling reaction promoted by (η2-propene)titanium
  作者：Christian Schäfer、Michel Miesch、Laurence Miesch

  DOI：10.1039/c2ob07049a

  日期：——

  Intramolecular reductive coupling of cycloalkanones tethered to alkynoates in the presence of (η2-propene)titanium was successfully performed to provide hydroxy-esters in a diastereoselective manner. Subsequent lactonization afforded angularly fused unsaturated tricyclic lactones which represent relevant substructures of numerous bioactive compounds.

  分子内还原偶联反应在(Λη²-丙烯)钛催化剂作用下成功地应用于与炔酸酯连接的环烷酮，以高对映选择性方式合成了羟基酯。随后的内酯化反应得到了角融合的不饱和三环内酯，这些结构是许多生物活性化合物的相关子结构。
• Preparation of 5-Membered Rings via Radical Addition- Translocation-Cyclization (RATC) Processes Mediated by Diethyl Thiophosphites
  作者：Christophe Lamarque、Florent Beaufils、Fabrice Dénès、Kurt Schenk、Philippe Renaud

  DOI：10.1002/adsc.201000852

  日期：2011.5

  is presented. The procedure requires the easily available terminal alkynes as starting materials as well as commercially and readily available reagents such as diethyl thiophosphite. The experimental procedure consists of a one‐pot process without any slow addition of one of the reagents.

  提出了一种形成带有官能化单环，稠合双环和螺环残基的硫代膦酸酯的实用方法。该方法需要容易获得的末端炔烃作为起始原料，以及商购可得的试剂，例如亚磷酸二乙酯。实验程序包括一锅法，不加任何一种试剂的缓慢加入。
• Thiophenol-Mediated 1,5-Hydrogen Atom Abstraction: Easy Access to Mono- and Bicyclic Compounds
  作者：Florent Beaufils、Fabrice Dénès、Barbara Becattini、Philippe Renaud、Kurt Schenk

  DOI：10.1002/adsc.200505211

  日期：2005.10

  method for cyclization of alkynes is described. The reaction cascade involves the intermolecular addition of a phenylthiyl radical to a terminal triple bond generating an alkenyl radical, followed by a 1,5-hydrogen atom transfer and a 5-exo-trig radical cyclization. This very efficient tin-free procedure allows one to prepare highly functionalized cyclopentane derivatives as well as fused bicyclic and

  描述了硫代苯酚介导的炔烃环化方法。反应级联反应涉及在分子间将苯基噻吩基分子间加成到末端三键上，从而产生烯基基团，然后进行1，5-氢原子转移和5- exo- trig自由基环化。这种非常有效的无锡程序使人们可以从容易获得的前体制备高度官能化的环戊烷衍生物以及稠合的双环和螺环化合物。在该环化过程中，将苯硫基部分掺入最终的环化产物中。这种功能化对于产品的进一步转化特别有吸引力。
• Intramolecular radical cyclization of silylacetylenic or olefinic α-iodo ketones: Application to the total synthesis of (±)-modhephene
  作者：Sha Chin-Kang、Jean Tsong-Shin、Wang Deh-Chi

  DOI：10.1016/s0040-4039(00)97460-4

  日期：——

  Silylacetylenic or olefinic α-iodo ketones were treated with tributyltin hydride and AIBN to give bicyclic ketones by an intramolecular α-carbonyl radical cyclization reaction. As an application of this radical cyclization reaction, the total synthesis of (±)-modhephene has been accomplished efficiently.

  用氢化三丁基锡和AIBN处理甲硅烷基或烯属α-碘酮，通过分子内α-羰基自由基环化反应得到双环酮。作为该自由基环化反应的一种应用，已经有效地完成了（±）-二苯乙烯的全合成。