4-methyldodec-1-yn-4-ol | 562836-62-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methyldodec-1-yn-4-ol
• 英文别名: 4-Methyldodec-1-YN-4-OL
• CAS: 562836-62-8
• 化学式: C₁₃H₂₄O
• 分子量: 196.333
• InChiKey: QGMQRJXVQPJHQF-UHFFFAOYSA-N

物化性质

• 沸点：
  292.0±13.0 °C(Predicted)
• 密度：
  0.874±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  14
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-methyldodec-1-yn-4-ol 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 tris(3,5-difluorophenyl)phosphine 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以62%的产率得到2-methyl-2-octyl-2,3-dihydrofuran
  参考文献：
  名称：

  A Rh(I)-Catalyzed Cycloisomerization of Homo- and Bis-homopropargylic Alcohols

  摘要：

  The ability to form rhodium-vinylidene complexes in situ from terminal alkynes has led to the development of a catalytic process, the cycloisomerization of homopropargylic and bis-homopropargylic alcohols to dihydrofurans and dihydropyrans. Among the transition metals that perform similar reactions, rhodium catalysts demonstrate the best chemoselectivity and turnover numbers to date. Both secondary and tertiary alcohols participate equally well. The presence of proparylic oxygen and nitrogen functionality, which potentially can be induced to ionize via formation of allenylidene metal complexes, is compatible with this catalyst. The formation of a 5-amino-dihydropyran which is not compatible with some of the previous catalysts proceeds in good yield with the rhodium catalysts. A substrate bearing a benzylic hydroxyl group adjacent to an electron-rich aromatic ring also participates without complications of ionization. The method provides access to useful aminosugars. A mechanism to account for the different selectivity of this catalyst as compared to others is proposed.

  DOI：

  10.1021/ja0344258
• 作为产物：
  描述：

  2-癸酮 、 3-氯丙炔 在 2,4,6-三甲基吡啶 、 二氯二茂钛 、 锰 、 三甲基氯硅烷 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以91%的产率得到4-methyldodec-1-yn-4-ol
  参考文献：
  名称：

  钛茂世（III）催化醛和酮的高效炔丙基化

  摘要：

  我们描述了一种新型方法，该方法用于在温和的反应条件下并与许多官能团相容，由钛茂（III）配合物催化广泛的醛和酮的炔丙基化。即使使用酮作为起始原料，也只能得到同炔丙醇，这在巴比尔型炔丙基化中是不常见的。

  DOI：

  10.1002/adsc.200900479

文献信息

• Titanium/Palladium-Mediated Regioselective Propargylation of Ketones using Propargylic Carbonates as Pronucleophiles
  作者：Alba Millán、Luis Álvarez de Cienfuegos、Ana Martín-Lasanta、Araceli G. Campaña、Juan M. Cuerva

  DOI：10.1002/adsc.201000655

  日期：2011.1.10

  for the synthesis of homopropargylic alcohols using propargylic carbonates as pronucleophiles is reported. The reaction is based on a combination of transition metal (palladium) and radical chemistry (titanium). The reaction takes place with an excellent regioselectivity and tolerates a great degree of substitution of the starting propargylic carbonate, thus being an interesting tool in the context

  报道了使用炔丙基碳酸酯作为亲核试剂的高效合成炔丙醇的方案。该反应基于过渡金属（钯）和自由基化学（钛）的组合。该反应以优异的区域选择性进行，并且可以耐受起始炔丙基碳酸酯的很大程度的取代，因此在合成有机化学的背景下是令人感兴趣的工具。
• Efficient Propargylation of Aldehydes and Ketones Catalyzed by Titanocene(III)
  作者：José Justicia、Iris Sancho-Sanz、Enrique Álvarez-Manzaneda、J. Enrique Oltra、Juan M. Cuerva

  DOI：10.1002/adsc.200900479

  日期：2009.10

  We describe a novel method for the propargylation of a wide range of aldehydes and ketones catalyzed by titanocene(III) complexes under mild reaction conditions and compatible with many functional groups. Homopropargylic alcohols are obtained as the sole products even when ketones are used as starting materials, which is unusual in Barbier-type propargylations.

  我们描述了一种新型方法，该方法用于在温和的反应条件下并与许多官能团相容，由钛茂（III）配合物催化广泛的醛和酮的炔丙基化。即使使用酮作为起始原料，也只能得到同炔丙醇，这在巴比尔型炔丙基化中是不常见的。
• CpTiCl₂ , an Improved Titanocene(III) Catalyst in Organic Synthesis
  作者：Esther Roldan-Molina、Natalia M. Padial、Luis Lezama、J. Enrique Oltra

  DOI：10.1002/ejoc.201801120

  日期：2018.11.25

  CpTiCl2, an improved titanocene(III) single‐electron transfer catalyst, under mild conditions provides excellent yields of homoallylic and homopropargylic alcohols in Barbier‐type allylation and propargylation reactions. Moreover, in the presence of a BOX ligand, it was capable of catalyzing enantioselective intramolecular allylations and propargylations (cyclizations) of ketones.

  CpTiCl 2是一种改进的钛茂（III）单电子转移催化剂，在温和的条件下，可在Barbier型烯丙基化和炔丙基化反应中提供均一和均丙醇的优异收率。此外，在BOX配体的存在下，它能够催化酮的对映选择性分子内烯丙基化和炔丙基化（环化）。
• A Rh(I)-Catalyzed Cycloisomerization of Homo- and Bis-homopropargylic Alcohols
  作者：Barry M. Trost、Young Ho Rhee

  DOI：10.1021/ja0344258

  日期：2003.6.1

  The ability to form rhodium-vinylidene complexes in situ from terminal alkynes has led to the development of a catalytic process, the cycloisomerization of homopropargylic and bis-homopropargylic alcohols to dihydrofurans and dihydropyrans. Among the transition metals that perform similar reactions, rhodium catalysts demonstrate the best chemoselectivity and turnover numbers to date. Both secondary and tertiary alcohols participate equally well. The presence of proparylic oxygen and nitrogen functionality, which potentially can be induced to ionize via formation of allenylidene metal complexes, is compatible with this catalyst. The formation of a 5-amino-dihydropyran which is not compatible with some of the previous catalysts proceeds in good yield with the rhodium catalysts. A substrate bearing a benzylic hydroxyl group adjacent to an electron-rich aromatic ring also participates without complications of ionization. The method provides access to useful aminosugars. A mechanism to account for the different selectivity of this catalyst as compared to others is proposed.