(E)-2-(hept-1-en-1-yl)pyridine | 211255-26-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (E)-2-(hept-1-en-1-yl)pyridine
• 英文别名: (E)-2-(1-heptenyl)pyridine；2-[(E)-hept-1-enyl]pyridine
• CAS: 211255-26-4
• 化学式: C₁₂H₁₇N
• 分子量: 175.274
• InChiKey: VPURUWYXFPCACW-RMKNXTFCSA-N

物化性质

• 沸点：
  120 °C(Press: 0.2 Torr)
• 密度：
  0.924±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2-(hept-1-en-1-yl)pyridine 在 acid 作用下， 生成 (E)-2-(3,3-dimethylbut-1-en-1-yl) pyridine
  参考文献：
  名称：

  Ru₃(CO)₁₂- and Rh₄(CO)₁₂-Catalyzed Reactions of Pyridylolefins or N-(2-Pyridyl)enamines with CO and Olefins. Carbonylation at Olefinic C−H Bonds

  摘要：

  This paper describes a study of the Ru-3(CO)(12)-catalyzed carbonylation at an olefinic C-K bond. The reaction of pyridylolefins with CO and ethylene in the presence of a catalytic amount of Ru-3(CO)(12) in toluene results in propionylation at an olefinic C-H bond in pyridylolefins. The carbonylation occurs regioselectively ata position gamma to the pyridine nitrogen. Transition-metal complexes other than Ru3(CO)12 that have thus far been examined exhibit no catalytic activity, and ethylene serves as the only olefin. A similar tendency has been noted in the previously reported carbonylation at a C-H bond in the benzene ring of pyridylbenzenes. This reaction can be also applied to N-(2-pyridyl)enamines, in which an olefin unit is separated from the pyridine ring by an sp(3)-nitrogen atom. The reaction of N-(2-pyridyl)enamines with CO and ethylene gives the corresponding ethyl ketones as the coupling products. Interestingly, Rh-4(CO)(12) also shows high catalytic activity in the case of N-(2-pyridyl)enamines. In addition, olefins such as propene, 1-hexene, 3,3-dimethyl-1-butene, styrene, cyclopentene, acryl acid methyl ester, ethyl vinyl ether, and trimethylvinylsilane can also be used. This is in sharp contrast to the case of the carbonylation at a C-H bond in pyridylbenzenes reported previously and to the results of pyridylolefins as mentioned above, where Ru-3(CO)(12) is the only active catalyst and hexene-cannot substitute for ethylene.

  DOI：

  10.1021/jo980335n
• 作为产物：
  描述：

  n-溴代已基三苯基膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 13.0h， 生成 (E)-2-(hept-1-en-1-yl)pyridine
  参考文献：
  名称：

  可调节的立体选择性烯烃的合成，方法是用不稳定的亚磷鎓盐处理活化的亚胺。

  摘要：

  各种容易获得的N-磺酰基亚胺在温和的条件下与不稳定的烷基化物进行烯化反应，从而以良好的收率获得了一系列1,2-二取代的烯烃，烯丙醇和烯丙基胺的Z-异构体和E-异构体。具有大于99：1的立体选择性。

  DOI：

  10.1039/c0cc04739b

文献信息

• Direct Wittig Olefination of Alcohols
  作者：Qiang-Qiang Li、Zaher Shah、Jian-Ping Qu、Yan-Biao Kang

  DOI：10.1021/acs.joc.7b02720

  日期：2018.1.5

  A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination

  描述了在有氧条件下使用醇作为廉价且清洁的氧化剂，使用醇在碱性条件下使用无醇过渡醇取代烯烃的方法。与相应的醇相比，由于醛的挥发性和聚合和自氧化倾向，因此醛相对较难处理。维蒂希酸根易于氧化成醛，因此形成均烯烃化产物。首次通过同时原位生成乙叉和乙叉的策略，无需预先制备醛或乙叉醇就将醇直接转移到烯烃中。因此，实现了二醇的二/单可控烯烃化。这种合成实用的方法已用于克级合成的药物，如DMU-212和白藜芦醇。
• Stereospecific Palladium-Catalyzed Cross-Coupling of (<i>E</i>)- and (<i>Z</i>)-Alkenylsilanolates with Aryl Chlorides
  作者：Scott E. Denmark、Jeffrey M. Kallemeyn

  DOI：10.1021/ja065988x

  日期：2006.12.1

  geometrically defined (E)- and (Z)-alkenyl- and styrylsilanolates with a wide variety of aromatic and heteroaromatic chlorides has been achieved. Under catalysis by bulky, biphenyl-derived phosphines and allylpalladium chloride, the (preformed, stable) potassium salts of di-, tri- and tetrasubstituted alkenyldimethylsilanols undergo high yielding and highly stereospecific coupling to aryl chlorides in THF or dioxane

  已经实现了几何定义的 (E)-和 (Z)-烯基-和苯乙烯基硅烷醇化物与多种芳族和杂芳族氯化物的交叉偶联。在庞大的联苯衍生的膦和烯丙基氯化钯的催化下，二、三和四取代的烯基二甲基硅烷醇的（预先形成的、稳定的）钾盐在 THF 或二恶烷中与芳基氯化物发生高产率和高度立体有择的偶联。多种官能团与这些反应条件相容，包括硝基、酯、酮和腈。(E)- 和 (Z)- 链烯基硅烷醇化物都具有几乎相同的速率和效率。
• Lim, Yeong-Gweon; Kang, Jung-Bu; Kim, Yong Hae, Journal of the Chemical Society. Perkin transactions I, 1998, # 4, p. 699 - 707
  作者：Lim, Yeong-Gweon、Kang, Jung-Bu、Kim, Yong Hae

  DOI：——

  日期：——
• Ruthenium-Mediated Regio- and Stereoselective Alkenylation of Pyridine
  作者：Masahiro Murakami、Seiji Hori

  DOI：10.1021/ja029829z

  日期：2003.4.1

  A novel alkenylation reaction of pyridine is developed. Heating a cationic ruthenium vinylidene complex [CpRu(=C=CHR)(PPh(3))(2)]PF(6) in pyridine at 100-125 degrees C for 24 h affords (E)-2-alkenylpyridine. Initially, pyridine coordinates to ruthenium by displacement of one of the phosphine ligands. Then, [2 + 2] heterocycloaddition occurs to form a four-membered ruthenacyclic complex. Deprotonation of the beta-hydrogen affords a neutral pi-azaallyl complex. Protonolysis furnishes the product. As a result, a vinylidene group is inserted into the alpha C-H bond of pyridine. The alkenylation reaction is made catalytic in ruthenium by the use of (alkyn-1-yl)silane as the vinylidene source. Treatment of (alkyn-1-yl)trimethylsilane with pyridine in the presence of a cationic ruthenium complex [CpRu(PPh(3))(2)]PF(6) affords the corresponding (E)-2-alkenylpyridine in good yield in a regio- and stereoselective manner.
• Ru₃(CO)₁₂- and Rh₄(CO)₁₂-Catalyzed Reactions of Pyridylolefins or <i>N</i>-(2-Pyridyl)enamines with CO and Olefins. Carbonylation at Olefinic C−H Bonds
  作者：Naoto Chatani、Yutaka Ishii、Yutaka Ie、Fumitoshi Kakiuchi、Shinji Murai

  DOI：10.1021/jo980335n

  日期：1998.7.1

  This paper describes a study of the Ru-3(CO)(12)-catalyzed carbonylation at an olefinic C-K bond. The reaction of pyridylolefins with CO and ethylene in the presence of a catalytic amount of Ru-3(CO)(12) in toluene results in propionylation at an olefinic C-H bond in pyridylolefins. The carbonylation occurs regioselectively ata position gamma to the pyridine nitrogen. Transition-metal complexes other than Ru3(CO)12 that have thus far been examined exhibit no catalytic activity, and ethylene serves as the only olefin. A similar tendency has been noted in the previously reported carbonylation at a C-H bond in the benzene ring of pyridylbenzenes. This reaction can be also applied to N-(2-pyridyl)enamines, in which an olefin unit is separated from the pyridine ring by an sp(3)-nitrogen atom. The reaction of N-(2-pyridyl)enamines with CO and ethylene gives the corresponding ethyl ketones as the coupling products. Interestingly, Rh-4(CO)(12) also shows high catalytic activity in the case of N-(2-pyridyl)enamines. In addition, olefins such as propene, 1-hexene, 3,3-dimethyl-1-butene, styrene, cyclopentene, acryl acid methyl ester, ethyl vinyl ether, and trimethylvinylsilane can also be used. This is in sharp contrast to the case of the carbonylation at a C-H bond in pyridylbenzenes reported previously and to the results of pyridylolefins as mentioned above, where Ru-3(CO)(12) is the only active catalyst and hexene-cannot substitute for ethylene.