3-Methyl-hex-4-yn-1-ol | 204760-59-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-Methyl-hex-4-yn-1-ol
• 英文别名: 3-Methylhex-4-yn-1-ol
• CAS: 204760-59-8
• 化学式: C₇H₁₂O
• 分子量: 112.172
• InChiKey: PHISVTQEWSMJFE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  3-Methyl-hex-4-yn-1-ol 在 palladium on activated charcoal 盐酸 、 正丁基锂 、 氢气 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 50.5h， 生成 (2RS,3RS)-2-methyl-3-<(1RS)-1,5-dimethylhexyl>cyclopentanone
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.

  DOI：

  10.1021/jo972186z
• 作为产物：
  描述：

  4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol 在 正丁基锂 、 草酰氯 、 三氟化硼乙醚 、 二甲基亚砜 、 三苯基膦 作用下， 生成 3-Methyl-hex-4-yn-1-ol
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.

  DOI：

  10.1021/jo972186z

文献信息

• Interligand Interactions Dictate the Regioselectivity of<i>trans</i>-Hydrometalations and Related Reactions Catalyzed by [Cp*RuCl]. Hydrogen Bonding to a Chloride Ligand as a Steering Principle in Catalysis
  作者：Stephan M. Rummelt、Karin Radkowski、Dragoş-Adrian Roşca、Alois Fürstner

  DOI：10.1021/jacs.5b01475

  日期：2015.4.29

  mode in the presence of [Cp*Ru(MeCN)3]PF6 (1) as the catalyst; however, the regioselectivity is often poor with unsymmetrical substrates. This problem can be solved upon switching to a catalyst comprising a [Ru-Cl] bond, provided that the acetylene derivative carries a protic functional group. The R3M unit is then delivered with high selectivity to the alkyne-C atom proximal to this steering substituent

  在 [Cp*Ru(MeCN)3]PF6 (1) 作为催化剂的存在下，内炔与 R3M-H（M = Si、Ge、Sn）的反应遵循非常规的反式加成模式；然而，不对称底物的区域选择性通常很差。如果乙炔衍生物带有质子官能团，则该问题可以通过改用包含 [Ru-Cl] 键的催化剂来解决。然后，R3M 单元以高选择性传递到该控制取代基附近的炔烃-C 原子。这种导向效应源于极化的 [Ru-Cl] 键与质子取代基进行氢键合的能力，这有助于将炔烃上传、激活和锁定在配位球内。氯化物与 -MR3 中心的额外配位体接触将进入的试剂定位在匹配的方向，从而转化为高区域选择性。所提出的负载催化剂内的二次相互作用与大量制备和光谱数据以及固态新型钌 π 配合物 10 和 11 的结构一致。此外，还提出了 [Ru(σ-锡烷)] 配合物 (12a) 的第一个 X 射线结构，它确实具有外围 Ru-Cl……MR3 接触；该加合物也证实炔烃反式加成化学可能涉及
• [EN] PROCESS FOR THE RUTHENIUM CATALYZED TRANS-SELECTIVE HYDROSTANNATION OF ALKYNES<br/>[FR] PROCÉDÉ D'HYDROSTANNATION TRANS-SÉLECTIVE D'ALCYNES PAR CATALYSE AU RUTHÉNIUM
  申请人：STUDIENGESELLSCHAFT KOHLE MBH

  公开号：WO2015059006A1

  公开（公告）日：2015-04-30

  The present invention refers to a process for the ruthenium-catalyzed trans-selective hydrostannation of alkynes and the so-obtained products. The inventive process makes use of a tin hydride which is reacted with an alkyne in the presence of a cyclopentadienyl-coordinated ruthenium catalyst.

  本发明涉及一种钌催化的烯烃选择性水锡化反应的方法以及所得到的产物。该创新方法利用一种锡氢化合物与烯烃在环戊二烯基配位的钌催化剂存在下发生反应。
• COMPOUND HAVING BRANCHED ALKYL OR BRANCHED ALKENYL, OPTICALLY ISOTROPIC LIQUID CRYSTAL MEDIUM AND OPTICAL ELEMENT
  申请人：Sagou Kouki

  公开号：US20130100369A1

  公开（公告）日：2013-04-25

  A liquid crystal compound with branched alkyl or branched alkenyl as represented by formula (1), a liquid crystal medium (a liquid crystal composition or a polymer/liquid crystal composite material) containing the liquid crystal compound, and an optical element containing the liquid crystal medium are described. In formula (1), R 1 is branched alkyl of C 3-20 or branched alkenyl of C 3-20 . The ring A 1 , A 2 , A 3 , A 4 or A 5 is 1,4-phenylene or 1,3-dioxane-2,5-diyl, for example. Z 1 , Z 2 , Z 3 and Z 4 are independently a single bond or C 1-4 alkylene, for example. Y 1 is fluorine, for example, m, n and p are independently 0 or 1, and 1≦m+n+p≦3.