12-methyltridec-11-en-1-yne | 1403588-58-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 12-methyltridec-11-en-1-yne
• 英文别名: 12-Methyltridec-11-en-1-yne
• CAS: 1403588-58-8
• 化学式: C₁₄H₂₄
• 分子量: 192.345
• InChiKey: QXUVLYDAJIPCKN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  14
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  12-methyltridec-11-en-1-yne 在 Pt(dba)2 、 双氧水 、 sodium hydroxide 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 31.0h， 生成 syn-15-methyl-1-phenylhexadec-14-ene-4,5-diol
  参考文献：
  名称：

  Enantiomerically Enriched Tris(boronates): Readily Accessible Conjunctive Reagents for Asymmetric Synthesis

  摘要：

  The catalytic enantioselective diboration of vinyl boronate esters furnishes chiral tris(boronates) in a selective fashion. Subsequent deborylative alkylation occurs in a diastereoselective fashion, both for intermolecular and intramolecular processes.

  DOI：

  10.1021/ja510081r
• 作为产物：
  描述：

  10-十一炔醇 在 正丁基锂 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 7.16h， 生成 12-methyltridec-11-en-1-yne
  参考文献：
  名称：

  Enantiomerically Enriched Tris(boronates): Readily Accessible Conjunctive Reagents for Asymmetric Synthesis

  摘要：

  The catalytic enantioselective diboration of vinyl boronate esters furnishes chiral tris(boronates) in a selective fashion. Subsequent deborylative alkylation occurs in a diastereoselective fashion, both for intermolecular and intramolecular processes.

  DOI：

  10.1021/ja510081r

文献信息

• Broad-Spectrum Catalysts for the Ambient Temperature Anti-Markovnikov Hydration of Alkynes
  作者：Le Li、Mingshuo Zeng、Seth B. Herzon

  DOI：10.1002/anie.201404320

  日期：2014.7.21

  Anti‐Markovnikov alkyne hydration provides a valuable route to aldehydes. Half‐sandwich ruthenium complexes ligated by 5,5′‐bis(trifluoromethyl)‐2,2′‐bipyridine are remarkably active for this transformation. In the presence of 2 mol % metal, a wide range of functionalized aliphatic and aromatic alkynes are hydrated in high yield at ambient temperature.

  抗马尔科夫尼科夫炔烃水合为醛的合成提供了有价值的途径。由5,5'-双（三氟甲基）-2,2'-联吡啶连接的半三明治钌络合物对于该转化非常有效。在2mol％金属的存在下，在环境温度下高产率地将多种官能化的脂族和芳族炔烃水合。
• Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes
  作者：Le Li、Seth B. Herzon

  DOI：10.1038/nchem.1799

  日期：2014.1

  There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes—often the inspiration for new synthetic transformations—are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades. Multifunctional catalysts typically process substrates and intermediates concurrently. Here, a strategy is described to separate catalytic activities in the time domain (temporal separation). Application of this strategy has led to the development of a method to effect the anti-Markovnikov reductive functionalization of terminal alkynes; such an approach may facilitate the development of other synthetic reaction cascades.

  目前，发展多步催化过程备受关注，其中一个或多个催化剂按顺序作用，以快速构建复杂分子结构。许多酶——通常是新合成转化的灵感来源——能够通过一系列离散的、机制上不同的催化步骤处理单一底物。在这里，我们描述了一种通过催化活性的时间分离来模拟这些自然反应级联的效率的方法。在这种方法中，单一催化剂按顺序展现多种催化活性，从而允许有效地通过级联路径处理底物。该设计策略的应用促成了一种方法，以实现末端炔烃的反马尔科夫尼科夫（线性选择性）还原官能化。时间分离的策略可能会促进其他高效合成反应级联的发展。多功能催化剂通常同时处理底物和中间体。在这里，描述了一种在时间领域分离催化活性的策略（时间分离）。该策略的应用促成了一种方法，以实现末端炔烃的反马尔科夫尼科夫还原官能化；如此方法可能会促进其他合成反应级联的发展。
• A Highly Active and Air-Stable Ruthenium Complex for the Ambient Temperature Anti-Markovnikov Reductive Hydration of Terminal Alkynes
  作者：Mingshuo Zeng、Le Li、Seth B. Herzon

  DOI：10.1021/ja501738a

  日期：2014.5.14

  partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate

  通过直接添加基于杂原子的亲核试剂将末端炔烃转化为功能化产物是催化的一个重要目标。我们报告了半夹心钌配合物 12 的设计、合成和机理研究，它是炔烃的反马尔科夫尼科夫还原水合的高活性催化剂。12 的关键设计元素涉及一个三齿氮基配体，其中包含一个半稳定的 3-（二甲氨基）丙基取代基。在中性条件下，二甲氨基取代基与钌中心协调，生成空气稳定的 18 电子 κ(3) 复合物。机理研究表明，二甲氨基取代基在反应介质中从钌中心部分解离（通过质子化），从而产生用于催化的空配位点。这些研究还表明，该取代基通过促进还原剂的活化来提高氢化活性。至少三个催化循环，包括甲酸的脱羧、炔烃的水合和中间体醛的氢化，在由 12 介导的反应中同时运行。 使用少至 2在环境温度下 mol % 为 12，并且配合物 12 在空气中稳定至少两周。本文概述的研究将 12 确立为迄今为止发现的用于反马尔科夫尼科夫还原水合的最活跃和最实用的催化剂，定义了
• Stereoselective Alkyne Hydrohalogenation by Trapping of Transfer Hydrogenation Intermediates
  作者：Manas Das、Trinadh Kaicharla、Johannes F. Teichert

  DOI：10.1021/acs.orglett.8b02055

  日期：2018.8.17

  A catalytically generated vinylcopper complex, the reactive intermediate of a copper(I)-catalyzed alkyne transfer hydrogenation, can be trapped by commercially available halogen electrophiles. In this manner, internal alkynes can stereoselectively be hydrohalogenated to the corresponding vinyl chlorides, bromides, and iodides.

  催化生成的乙烯基铜络合物是铜（I）催化的炔烃转移氢化的反应中间体，可被市售的卤素亲电子试剂捕获。以这种方式，内部炔烃可以被立体选择性地氢卤化为相应的氯乙烯，溴化物和碘化物。
• Regioselective Reductive Hydration of Alkynes To Form Branched or Linear Alcohols
  作者：Le Li、Seth B. Herzon

  DOI：10.1021/ja307145e

  日期：2012.10.24

  The regioselective reductive hydration of terminal alkynes using two complementary dual catalytic systems is described. Branched or linear alcohols are obtained in 75-96% yield with >= 25:1 regioselectivity from the same starting materials. The method is compatible with terminal, di-, and trisubstituted alkenes. This reductive hydration constitutes a strategic surrogate to alkene oxyfunctionalization and may be of utility in multistep settings.