1-(methylthio)-2-cyclohexylacetylene | 130612-91-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫基化合物
• 英文名称: 1-(methylthio)-2-cyclohexylacetylene
• 英文别名: 2-Methylsulfanylethynylcyclohexane
• CAS: 130612-91-8
• 化学式: C₉H₁₄S
• 分子量: 154.276
• InChiKey: BFEYLFZWYJDDJL-UHFFFAOYSA-N

物化性质

• 沸点：
  235.2±23.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(methylthio)-2-cyclohexylacetylene 在 甲醇 、 三甲基溴硅烷 、 叔丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (Z)-3-Cyclohexyl-2-methylsulfanyl-acrylic acid benzyl ester
  参考文献：
  名称：

  A stereoselective synthesis of α-halo vinyl sulfides and their applications in organic synthesis

  摘要：

  alpha -Halo vinyl sulfides have been synthesized stereoselectively via the addition of the in situ! generated hydrogen halide to acetylenic thioether. alpha -Halo vinyl sulfides are versatile substrates that can undergo many important transformations. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00556-1
• 作为产物：
  描述：

  环己基乙炔 以28%的产率得到
  参考文献：
  名称：

  Narasaka Koichi, Hayashi Yujiro, Shimadzu Hideshi, Niihata Shigeo, J. Amer. Chem. Soc., 114 (1992) N 23, S 8869-8885

  摘要：

  DOI：

文献信息

• An Asymmetric Redox Arylation: Chirality Transfer from Sulfur to Carbon through a Sulfonium [3,3]-Sigmatropic Rearrangement
  作者：Dainis Kaldre、Boris Maryasin、Daniel Kaiser、Oliver Gajsek、Leticia González、Nuno Maulide

  DOI：10.1002/anie.201610105

  日期：2017.2.13

  4‐chirality transfer from sulfur to a carbon stereocenter through a sulfonium [3,3]‐sigmatropic rearrangement. This reaction delivers α‐arylated thioesters and amides under mild conditions in an atom‐economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain

  据报道，乙酰胺和硫代炔与手性亚砜的一般不对称氧化还原芳基化反应。这是通过sulfur [3,3]-σ重排从硫到碳立体中心的一般1,4-手性转移的第一个例子。该反应在温和条件下以原子经济的方式提供α-芳基化的硫酯和酰胺。产物以高收率形成，对映体比例高达99.5：0.5。量子化学计算提出了从硫到碳的手性转移的机理，并解释了实验观察到的对映选择性与催化剂和底物的相关性。
• Asymmetric [2+2] Cycloaddition Reaction between α,β-Unsaturated Acid Derivatives and Alkynyl or Alkenyl Sulfides Catalyzed by a Chiral Titanium Reagent
  作者：Yujiro Hayashi、Koichi Narasaka

  DOI：10.1246/cl.1990.1295

  日期：1990.8

  Asymmetric [2+2] cycloaddition reaction between 3-(acryloyl)-1,3-oxazolidin-2-one derivatives and alkynyl or alkenyl sulfides proceeds by the use of a chiral titanium reagent to give the corresponding cyclobutene or cyclobutane derivatives in high enantioselectivity.

  3-(丙烯酰基)-1,3-恶唑烷-2-酮衍生物与炔基或烯基硫化物之间的不对称[2+2]环加成反应通过使用手性钛试剂进行，以高对映选择性得到相应的环丁烯或环丁烷衍生物.
• Direct Synthesis of α‐Amino Acid Derivatives by Hydrative Amination of Alkynes
  作者：Minghao Feng、Roberto Tinelli、Ricardo Meyrelles、Leticia González、Boris Maryasin、Nuno Maulide

  DOI：10.1002/anie.202212399

  日期：2023.1.2

  α-Amino acid derivatives are key components of the molecules of life. A hydrative amination of ynamides/thioalkynes under metal-free and mild conditions has been developed. This practical strategy offers a new and convenient avenue for the synthesis of α-amino acid derivatives using readily available sulfinamides as nitrogen sources. Computational studies suggest that the reaction is enabled by a new

  α-氨基酸衍生物是生命分子的关键组成部分。已经开发了在无金属和温和条件下炔胺/硫代炔烃的水合胺化。这种实用的策略为使用现成的亚磺酰胺作为氮源合成 α-氨基酸衍生物提供了一种新的便捷途径。计算研究表明，该反应是由一种新型硫鎓 [2,3]-sigmatropic 重排促成的。
• Hydroformylation of Alkynyl Sulfides: A Stereo‐ and Regioselective Route to α‐Sulfenyl Acroleins
  作者：Patrick Wagner、Mihaela Gulea、Nicolas Girard

  DOI：10.1002/adsc.202301349

  日期：2024.3.19

  sulfides. Additionally, one can take advantage of the possibility of the sulfur oxidation to obtain an alkenyl sulfoxide or sulfone, and so altering the electronic behavior of the carbon-carbon double bond. So far, the synthesis of α-sulfanyl acroleins (Scheme 1) is mainly based on general methods involving the incorporation of the sulfur function into an α,β-unsaturated aldehyde as a nucleophile (Scheme 1

  描述了在温和条件下铑催化的炔基硫醚的加氢甲酰化反应。该方法可以获得具有良好区域选择性（α/β 比例高达 89/11）的 α-硫基丙烯醛，并且适用于各种取代的底物。它甚至对更复杂的底物（例如半胱氨酸和胆固醇衍生物）也有效。为了证明所得产物的合成潜力，选择(Z)-3-环己基-2-甲基硫基丙烯醛为例，将其硫原子选择性氧化成相应的亚砜或砜。在氧化过程中，酸促进双键从 (Z) 异构化为 (E)。然后将获得的三种硫基、亚磺酰基和磺酰基官能化丙烯醛用作亲二烯体以制备环己烯甲醛。
• Asymmetric [2 + 2] cycloaddition reaction catalyzed by a chiral titanium reagent
  作者：Koichi Narasaka、Yujiro Hayashi、Hideshi Shimadzu、Shigeo Niihata

  DOI：10.1021/ja00049a020

  日期：1992.11

  In the presence of certain Lewis acids, alkenes containing an alkylthio group (for example, ketene dithioacetals, alkenyl sulfides, alkynyl sulfides, and allenyl sulfides) react with electron deficient olefins to give the corresponding cyclobutane, cyclobutene, or methylene cyclobutane derivatives. By employing a chiral titanium catalyst generated in situ from dichlorodiisopropoxytitanium and a tartrate-derived chiral diol, the [2 + 2] cycloaddition reaction proceeds with high enantioselectivity.