3-methoxy-3-hexene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methoxy-3-hexene
• 英文别名: 3-Methoxyhex-3-ene；3-methoxyhex-3-ene
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: RWRGGFPFAHYJKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  甲醇 、 3-己炔 在 AuCl₃ nanoparticles on wool 作用下， 反应 2.0h， 生成 3-methoxy-3-hexene 、 diethylethylene glycol dimethyl ether
  参考文献：
  名称：

  羊毛上的金纳米粒子与分子金催化剂的比较研究

  摘要：

  将氯化金纳米颗粒的催化活性与两种分子金 (I) 氯化膦配合物在甲醇添加到 3-己炔中的活性进行比较。膦是三苯基膦和与双吡啶酮相关的大块 6,8-双-(4-二甲氨基-苯基)-3-甲基-9-氧代-7-苯基-3-氮杂-7-磷酸-双环[3.3.1]壬聚糖-1,5-二羧酸二甲酯。大配体的使用使得加成反应对烯醇产物具有选择性，这意味着不会向反应过程中产生的烯烃添加甲醇或水。相比之下，使用氯化三苯基膦金 (I) 可合成多种产品。膦在反应过程中分解，形成金纳米颗粒，发现其无催化活性。人工生产的金纳米粒子也被证明是无活性的。相比之下，沉积在羊毛上的氯化金纳米粒子的活性与之前测试的含金膦催化剂相当。与文献结果相比，观察到的总体活性较低，表明可以优化所选的操作条件。

  DOI：

  10.1007/s13404-012-0076-3

文献信息

• Unexpected Anion Effect in the Alkoxylation of Alkynes Catalyzed by N-Heterocyclic Carbene (NHC) Cationic Gold Complexes
  作者：Luca Biasiolo、Marina Trinchillo、Paola Belanzoni、Leonardo Belpassi、Vincenzo Busico、Gianluca Ciancaleoni、Angela D'Amora、Alceo Macchioni、Francesco Tarantelli、Daniele Zuccaccia

  DOI：10.1002/chem.201404539

  日期：2014.11.3

  The intermolecular alkoxylation of alkynes is the oldest application of cationic gold(I) catalysts; however, no systematic experimental data about the role of the anion are available. In this contribution, the role of the anion in this catalytic reaction as promoted by a N‐heterocyclic carbene‐based gold catalyst, [(NHC)AuX] (X=BARF−, BF4−, OTf−, OTs−, TFA−, or OAc−) is analyzed, through a combined

  炔烃的分子间烷氧基化是阳离子金（I）催化剂的最古老应用；但是，尚无有关阴离子作用的系统实验数据。在这方面的贡献，该阴离子在这个催化反应作用，作为促进通过N-杂环基卡宾-金催化剂，[（NHC）AUX]（X = BARF -，BF 4 - ，光学传递函数- ，在职培训计划-，TFA -或OAC -）是通过组合实验（NMR光谱）和理论（DFT计算）方法进行分析的。最重要的因素似乎是在亲核攻击中从甲醇中提取质子的能力，而这种能力与阴离子的碱性有关。另一方面，阴离子的高配位能力或碱性会通过防止炔烃配位或在溶液中形成过多的游离甲醇而使催化性能恶化，这会毒化催化剂。OTS的中间协调功率和碱度-阴离子提供最好的折衷来实现高效催化。
• Toward Optimizing the Performance of Homogeneous L-Au-X Catalysts through Appropriate Matching of the Ligand (L) and Counterion (X^–)
  作者：Luca Biasiolo、Alessandro Del Zotto、Daniele Zuccaccia

  DOI：10.1021/acs.organomet.5b00308

  日期：2015.5.11

  The effects of the ligand (L) and counterion (X-) are considered the two most important factors in homogeneous gold catalysis, but a rational understanding of their synergy/antagonism is still lacking. In this work, we synthesized a set of 16 gold-complexes of the type L-Au-X that differ as follows: (i) L = PPh3 (Li), P(Bu-t)(3) (L2), tris(3,5-bis(trifluoromethyl)phenyl)phosphine (PArF, L3), and 1,3-bis (2,6-diisopropylphenyl)imidazol-2-ylidene (NHC, L4), with the deliberate purpose of varying the electron withdrawing ability of the ligand, and (ii) X- = BF4-, OTf-, OTs-, and TFA(-), which have various coordinating abilities, basicities, and hydrogen bond acceptor powers. All these catalysts were tested in two different model reactions: the cycloisomerization of N-(prop-2-ynyl)benzamide to 2-phenyl-5-vinylidene-2-oxazoline and the methoxylation of 3-hexyne. The main results are that the choice of the most efficient L-Au-X catalyst for a given process should not be made by evaluating the properties of L and X- alone, but rather based on their best combination. For NHC-Au-X, the noncoordinating and weakly basic anions (such as BF4- and OTf-) have been recognized as the best choice for the cycloisomerization of N-(prop-2-ynyl)benzamide. On the other side, the intermediate coordinating ability and basicity of OTs- provide the best compromise for achieving an efficient methoxylation of 3-hexyne. A completely different trend is found in the case of complexes bearing phosphanes: OTs- and TFA(-) have been found to accelerate the c-ydoisomerization of N-(prop-2-ynyl)benzamide, and BF4- and OTf- are suitable for the methoxylation of 3-hexyne. A possible explanation of the observed differences between phosphane and NBC ancillary ligands might be found in the higher affinity of the counterion (especially OTs-) for the gold fragment for phosphane instead of NHC.
• Extensive Experimental and Computational Study of Counterion Effect in the Reaction Mechanism of NHC-Gold(I)-Catalyzed Alkoxylation of Alkynes
  作者：Marina Trinchillo、Paola Belanzoni、Leonardo Belpassi、Luca Biasiolo、Vincenzo Busico、Angela D’Amora、Lorenzo D’Amore、Alessandro Del Zotto、Francesco Tarantelli、Angela Tuzi、Daniele Zuccaccia

  DOI：10.1021/acs.organomet.5b00925

  日期：2016.3.14

  Herein, we synthesized and characterized through NMR and X-ray techniques a new set of [(NHC)-Au-X] complexes (NHC = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene), differing in the counterion X (X = OMs , NO3 , ClO4 , 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoate (PFHp )). All of these complexes, together with those already known having NTf2 and phthalimide (ptm ) as counterions, were tested as catalysts in the methoxylation of 3-hexyne. The results were analyzed together with those obtained previously. The values of activation parameters (Delta H-? and Delta S-?) for different anions are also reported. The overall catalytic and kinetic evidence, together with an extensive computational work, confirm the general mechanistic picture given recently in which the anion plays an active role in all steps of the reaction mechanism: pre-equilibrium, nucleophilic attack, and protodeauration. Medium-coordinating anions (OMs , OTs ) containing a highly symmetric anchoring group give the best catalytic performances. This is due to the following reasons: (a) the pre-equilibrium is shifted toward the outer sphere ion pair, (b) their characteristic basicity promotes the nucleophilic attack, and (c) the possible paths leading to the deactivation of the catalyst are inhibited. These highly symmetric tridentate anions destabilize the unreactive tricoordinated gold species, which instead may be formed by anions with a planar anchoring group, such as PFHp and TFA . A general trend between coordinating ability and catalytic performances in the alkoxylation of alkynes may be established only when the geometric features of the anion are taken into account. The role of the anion has been also investigated in connection with the nature of the nucleophile. In particular, when the alcohol is a poor nucleophile, a large difference in reactivity is observed, while the use of suitably functionalized alcohols, which may contribute to polarizing the -OH bond through intramolecular interactions, flattens the anion effect.
• Gold nanoparticles on wool in a comparative study with molecular gold catalysts
  作者：Thomas Borrmann、Teck Hock Lim、Hannah Cope、Kerstin Lucas、Michael Lorden

  DOI：10.1007/s13404-012-0076-3

  日期：2013.3

  catalytically inactive. Artificially produced gold nanoparticles also proved to be inactive. In contrast, gold chloride nanoparticles deposited on wool were active comparable to the gold phosphine-containing catalysts tested previously. Overall activities observed were low compared to results from the literature suggesting that the operating conditions chosen could be optimised.

  将氯化金纳米颗粒的催化活性与两种分子金 (I) 氯化膦配合物在甲醇添加到 3-己炔中的活性进行比较。膦是三苯基膦和与双吡啶酮相关的大块 6,8-双-(4-二甲氨基-苯基)-3-甲基-9-氧代-7-苯基-3-氮杂-7-磷酸-双环[3.3.1]壬聚糖-1,5-二羧酸二甲酯。大配体的使用使得加成反应对烯醇产物具有选择性，这意味着不会向反应过程中产生的烯烃添加甲醇或水。相比之下，使用氯化三苯基膦金 (I) 可合成多种产品。膦在反应过程中分解，形成金纳米颗粒，发现其无催化活性。人工生产的金纳米粒子也被证明是无活性的。相比之下，沉积在羊毛上的氯化金纳米粒子的活性与之前测试的含金膦催化剂相当。与文献结果相比，观察到的总体活性较低，表明可以优化所选的操作条件。