1-(hex-1-yn-1-yl)cyclohept-1-ene | 1400914-98-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-(hex-1-yn-1-yl)cyclohept-1-ene
• CAS: 1400914-98-8
• 化学式: C₁₃H₂₀
• 分子量: 176.302
• InChiKey: SDXHYNGXNNXXSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1-(hex-1-yn-1-yl)cyclohept-1-ene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以73%的产率得到1-(hex-1-yn-1-yl)-8-oxabicyclo[5.1.0]octane
  参考文献：
  名称：

  Polyoxometalate-Gold(I)/H⁺ Complexes: Air-Stable, Efficient, Polyvalent, and Bifunctional Catalysts

  摘要：

  Gold(I)/H+-polyoxometalate hybrids, with general formula [POM](x-)[H](x-1)(+)[R3PAu(MeCN)](+), were synthesized and fully characterized by P-31 and Si-29 MAS or liquid NMR, FT-IR, and mass spectroscopy. All these polyoxometalate gold(I) complexes exhibited excellent catalytic activity and selectivity compared to standard homogeneous gold catalysts in a large range of reactions. The variation of the ligand and the polyoxometalate nature around gold(I) also highlighted the flexibility and the multifunctionality of such catalysts, as well as their recyclability.

  DOI：

  10.1021/acs.organomet.5b00656
• 作为产物：
  描述：

  环庚酮 在 正丁基锂 、 三氯氧磷 作用下， 以 四氢呋喃 、 吡啶 、 正己烷 为溶剂， 反应 4.5h， 生成 1-(hex-1-yn-1-yl)cyclohept-1-ene
  参考文献：
  名称：

  Synthesis, Characterization, and Catalytic Activity of Alcohol-Functionalized NHC Gold(I/III) Complexes

  摘要：

  A series of alcohol-functionalized NHC gold(I/III) complexes of the types [(L)Au(Cl or NTf2)] and [(L)AuCl3] (L = IPrEtOH, (1, 4, 5), IMesEtOH (2, 6), IMeEtOH (3, 7)) was readily synthesized and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The catalytic activity of the new complexes was assessed and compared with that of other gold catalysts, in the tandem 3,3-rearrangement-Nazarov reactions of enynyl acetate and the rearrangement reaction of alkynyloxirane. The new complexes appeared to be dual-site catalysts in both transformations, thanks to the presence of the primary alcohol function tethered to the NHC ligands.

  DOI：

  10.1021/om500240h

文献信息

• Regio- and Stereoselective Hydrosilylation of 1,3-Enynes Catalyzed by Palladium
  作者：Hui Zhou、Christina Moberg

  DOI：10.1021/ol4001334

  日期：2013.4.5

  In the presence of Pd(0) and a phosphine, hydrosilylation of 1,3-enynes with Me2SiHCl proceeds to yield dienylsilanes with the silicon function added to the internal alkyne carbon atom and with (E)-configuration of newly formed olefinic bond. The silanols isolated after hydrolysis of the primarily obtained products serve as precursors to conjugated dienes with different substitution patterns.

  在Pd（0）和磷化氢的存在下，1,3-烯炔与Me 2 SiHCl的硅氢加成反应会生成二烯基硅烷，其硅官能团添加到内部炔烃碳原子上，并且新形成的烯键具有（E）-构型。最初获得的产物水解后分离出的硅烷醇用作具有不同取代方式的共轭二烯的前体。
• Tunable Cross Coupling of Silanols: Selective Synthesis of Heavily Substituted Allenes and Butadienes
  作者：Hui Zhou、Christina Moberg

  DOI：10.1021/ja3070717

  日期：2012.9.26

  substitution patterns are readily obtained by palladium-catalyzed silaboration of 1,3-enynes followed by Suzuki-Miyaura cross coupling with aryl bromides. Subsequent Hiyama-Denmark cross coupling with aryl iodides provides either 1,3- or 1,2-dienes in high yields. The site selectivity can be fully controlled by the choice of activator used in the coupling reaction. In the presence of strong bases such as

  具有广泛取代模式的 1,3-二烯基-2-硅烷醇很容易通过钯催化的 1,3-烯炔硅化，然后 Suzuki-Miyaura 与芳基溴化物交叉偶联而获得。随后 Hiyama-Denmark 与芳基碘化物交叉偶联以高产率提供 1,3- 或 1,2- 二烯。通过选择偶联反应中使用的活化剂可以完全控制位点选择性。在强碱如 NaOt-Bu、KOt-Bu 和 NaH 存在下，1,2-二烯通过烯丙基重排形成。相比之下，四和三取代的 1,3-二烯的立体和站点选择性形成是由分别使用 Ag(2)O 和 Bu(4)NF·3H(2)O 作为活化剂造成的。在 100 °C 的微波加热下，碱基介导的交叉偶联大大加速，并在一小时或更短的时间内完成。
• Silver(I)-Catalyzed Cascade: Direct Access to Furans from Alkynyloxiranes
  作者：Aurélien Blanc、Katharina Tenbrink、Jean-Marc Weibel、Patrick Pale

  DOI：10.1021/jo900483m

  日期：2009.6.5

  Functionalized furans are conveniently formed by a new silver(I)-catalyzed reaction of alk-1-ynyl oxiranes in the presence of p-toluenesulfonic acid and methanol. Evidence supported a cascade mechanism.
• Synthesis, Characterization, and Catalytic Activity of Cationic NHC Gold(III) Pyridine Complexes
  作者：Serena Orbisaglia、Béatrice Jacques、Pierre Braunstein、Damien Hueber、Patrick Pale、Aurélien Blanc、Pierre de Frémont

  DOI：10.1021/om400338k

  日期：2013.8.12

  A series of cationic gold(I/III) pyridine complexes of the type [(L)Au(pyr)](PF6) and [(L)AuCl2(pyr)](PF6), where L = IPr, (1, 5); L = IMes (2, 6); L = (IBu)-Bu-t, (3, 7); L = ICy (4, 8); and L = PPh3, (9, 10), were synthesized and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The stability of the new complexes and their catalytic activity in five well-established organic transformations were assessed.
• Mechanistic Studies and Improvement of Coinage Metal-Catalyzed Transformation of Alkynyloxiranes to Furans: An Alcohol Addition−Cyclization−Elimination Cascade
  作者：Aurélien Blanc、Katharina Tenbrink、Jean-Marc Weibel、Patrick Pale

  DOI：10.1021/jo9008172

  日期：2009.8.7

  In the presence of alcohol Ag or Au salts or complexes catalyze the conversion of alkynyloxiranes to substituted furans. Both-catalysts are effective, and a large furan diversity can be obtained in high yield with one or the other catalyst. Mechanistic studies revealed that a cascade pathway and not the sometimes reported direct intra molecular nucleophilic addition of oxirane oxygen atom to intermediate acetylene-metal pi-complex occurs. Under the defined conditions, the intermediate formation of epoxide opening products has been identified. Depending on the catalyst, one or both of the latter cyclized to dihydrofurans, and further elimination of the alcohol led to the corresponding furans. These results highlight the duality between oxophilicity and alkynophilicity of Ag or Au salts.