1-hexynyl methyl selenide | 39556-65-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1-hexynyl methyl selenide
• 英文别名: 1-(methylseleno)-1-hexyne；2-butylethynyl methyl selenide；hex-1-yn-1-yl(methyl)selane；1-Methylselenohex-1-in；1-methylselanyl-hex-1-yne；InChI=1/C7H12Se/c1-3-4-5-6-7-8-2/h3-5H2,1-2H；1-methylselanylhex-1-yne
• CAS: 39556-65-5
• 化学式: C₇H₁₂Se
• 分子量: 175.132
• InChiKey: XPISPLWJKHRTOI-UHFFFAOYSA-N

物化性质

• 沸点：
  194.7±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.89
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-hexynyl methyl selenide 在 sodium hydroxide 、 lithium aluminium tetrahydride 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 3.75h， 生成 (E)-hex-1-en-1-ylcyclohexane
  参考文献：
  名称：

  A stereoselective synthesis of 1,2-disubstituted alkenyl selenides via hydroboration-iodination of internal alkylselenoacetylenes with dicyclohexylborane

  摘要：

  Selenoalkenyldicyclohexylboranes, prepared conveniently via hydroboration of internal alkylselenoacetylenes with dicyclohexylborane followed by iodination under basic conditions, produce cis/trans 1,2-disubstituted alkenyl selenides (1 and 2), which provide a general method for synthesis of cis/trans disubstituted alkenyl selenides containing a cyclohexyl group.

  DOI：

  10.1016/0022-328x(96)06417-0
• 作为产物：
  描述：

  二甲基二硒醚 、 1-己炔 在 正丁基锂 作用下， 生成 1-hexynyl methyl selenide
  参考文献：
  名称：

  Asymmetric [2 + 2] cycloaddition reaction catalyzed by a chiral titanium reagent

  摘要：

  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.

  DOI：

  10.1021/ja00049a020

文献信息

• Redox-Neutral Synthesis of Selenoesters by Oxyarylation of Selenoalkynes under Mild Conditions
  作者：Lucas L. Baldassari、Anderson C. Mantovani、Samuel Senoner、Boris Maryasin、Nuno Maulide、Diogo S. Lüdtke

  DOI：10.1021/acs.orglett.8b02544

  日期：2018.9.21

  selenoalkynes through an acid-catalyzed, redox-neutral oxyarylation reaction is reported. Brønsted acid activation of a selenoalkyne leads to a selenium-stabilized vinyl cation, which is captured by an aryl sulfoxide and undergoes sigmatropic rearrangement to deliver the final α-arylated selenoester product. Computational studies have been carried out to elucidate the nature of the Se-stabilized carbocation

  据报道，从硒代炔烃开始，通过酸催化的，氧化还原-中性的氧化芳基化反应温和合成硒酸酯的方法。硒炔的布朗斯台德酸活化会生成硒稳定的乙烯基阳离子，该乙烯基阳离子会被芳基亚砜捕获并进行σ重排，从而生成最终的α-芳基硒酸酯产物。已经进行了计算研究以阐明硒稳定的碳正离子的性质。
• Addition of hydrogen halides to acetylenic selenides. Synthesis of 1-halo-1-selenoalkenes
  作者：João V. Comasseto、Paulo H. Menezes、Helio A. Stefani、Gilson Zeni、Antônio L. Braga

  DOI：10.1016/0040-4020(96)00505-4

  日期：1996.7

  Acetylenic selenides react with HX (X=Cl, Br, I) at room temperature to give 1-halo-1-selenoalkenes in good yields. The 1-iodo-1-selenoalkenes were transformed into the corresponding vinylic organometallics (M=Zn, Cu, Cr).

  乙炔硒化物在室温下与HX（X = Cl，Br，I）反应以高收率得到1-卤-1-硒烯。将1-碘-1-硒烯转化为相应的乙烯基有机金属化合物（M = Zn，Cu，Cr）。
• First Example of Alkynyliodonium Tosylates coupling with 1,1-Bimetalloalkenes of Selenium and Zirconium
  作者：Ai-Ming Sun、Xian Huang

  DOI：10.1039/a801589i

  日期：——

  Hydrozirconation of internal acetylenic selenides afforded 1,1-bimetalloalkenes, (E)-α-selanylvinylzirconium, which can cross-couple with alkynyliodonium tosylates directly in the presence of Pd(PPh3)4 as the catalyst.

  在 Pd(PPh3)4 作为催化剂存在的情况下，内部乙炔硒化氢锆反应生成了 1,1-双金属烷烃 (E)-α-乙炔硒化氢锆，它可以直接与炔基碘鎓对甲苯磺酸盐发生交叉耦合。
• Ligand-free, catalytic and regioselective hydroboration of selenoalkynes
  作者：Lucas L. Baldassari、Kelvin S. Santos、Camila P. Ebersol、Diogo S. Lüdtke、Angélica V. Moro

  DOI：10.1039/d0cy01379j

  日期：——

  The copper-catalyzed hydroboration of selenoalkynes in a regio- and stereoselective fashion is reported, delivering selenium-containing vinylboronate products in good yields. The reported protocol fills an important gap in the literature with respect to the synthesis of a valuable class of compounds, which is difficult to obtain otherwise.

  据报道，铜炔化合物以区域和立体选择性方式催化硼氢化硒代炔烃，从而以良好的产率提供了含硒的乙烯基硼酸酯产品。在合成有价值的一类化合物方面，已报道的方案填补了文献中的重要空白，否则很难获得。
• Stereo‐ and Regioselective Cu‐Catalyzed Hydroboration of Alkynyl Chalcogenoethers
  作者：Isadora M. Oliveira、Henrique A. Esteves、Mariana P. Darbem、Arthur Sartorelli、Thiago C. Correra、André F. Rodrigues‐Oliveira、Daniel C. Pimenta、Julio Zukerman‐Schpector、Flávia Manarin、Hélio A. Stefani

  DOI：10.1002/cctc.202000395

  日期：2020.7.6

  A mild stereo‐ and regioselective Cu‐catalyzed hydroboration method for the synthesis of (Z)‐seleno‐alkenyl boronates and (Z)‐thio‐alkenylboronates from internal alkynes in the presence of commercially available B2pin2 is presented. This highly selective transformation relies on the use of N‐heterocyclic carbene (NHC) complex IPrCuCl as the active catalytic species. We also explore the functionalization

  提出了一种温和的立体和区域选择性铜催化加氢硼化方法，该方法可在市售B 2 pin 2存在下从内部炔烃合成（Z）-硒代烯基硼酸酯和（Z）-硫代烯基硼酸酯。这种高度选择性的转化依赖于使用N-杂环卡宾（NHC）络合物IPrCuCl作为活性催化物质。我们还探讨了通过氧化获得的烯基硼酸酯的功能化，从而得到α-硫族元素基酮，这是合成更复杂的含硫族元素分子的有用组成部分。

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