1-(trimethylsilyl)-8-phenyl-1,3,5,7-octatetrayne | 596122-61-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(trimethylsilyl)-8-phenyl-1,3,5,7-octatetrayne
• 英文别名: 1-trimethylsilyl-8-phenyl-1,3,5,7-nonatetrayne；Silane, trimethyl(8-phenyl-1,3,5,7-octatetraynyl)-；trimethyl(8-phenylocta-1,3,5,7-tetraynyl)silane
• CAS: 596122-61-1
• 化学式: C₁₇H₁₄Si
• 分子量: 246.384
• InChiKey: QVMIMLYTBWBHNL-UHFFFAOYSA-N

物化性质

• 沸点：
  332.7±25.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.93
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 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-(trimethylsilyl)-8-phenyl-1,3,5,7-octatetrayne 在 水 、 potassium carbonate 、 copper(II) sulfate 、 维生素 C 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 1-Benzyl-4-(6-phenyl-hexa-1,3,5-triynyl)-1H-[1,2,3]triazole
  参考文献：
  名称：

  Regioselective Trapping of Terminal Di-, Tri-, and Tetraynes with Benzyl Azide

  摘要：

  The reaction of benzyl azide with terminal di-, tri-, and tetraynes appended with a range of functional groups has been explored. Standard reaction conditions for BnN3 catalyzed by CuSO(4)(.)5H(2)O gave alkynyl, butadiynyl, and hexatriynyl triazoles in moderate to good yields. The reaction proceeds regioselectively as determined by the X-ray crystallographic analysis of three derivatives (1c, 1d, and 3c), and no evidence of multiple azide addition to the polyyne framework is observed.

  DOI：

  10.1021/ol062522a
• 作为产物：
  描述：

  (E)-1-chloro-4-phenyl-1-buten-3-yne 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 15.0h， 生成 1-(trimethylsilyl)-8-phenyl-1,3,5,7-octatetrayne
  参考文献：
  名称：

  Highly Efficient and Selective Synthesis of Conjugated Triynes and Higher Oligoynes of Biological and Materials Chemical Interest via Palladium-Catalyzed Alkynyl−Alkenyl Coupling

  摘要：

  Iteration of a Pd-catalyzed reaction of alkynyl- and oligoynylzincs with (E)-ICH-CHCI followed by metalation-termination with electrophiles(E) has provided a linear route to conjugated tri- and tetraynes, and Pd-catalyzed monoalkynylation of 1,1-dibromoenynes accompanied by dehydrobromination has provided a convergent route to conjugated tri-, tetra-, and pentaynes. Both display unprecedented high efficiency and selectivity.

  DOI：

  10.1021/ol0623825

文献信息

• Alkyne Migration in Alkylidene Carbenoid Species: A New Method of Polyyne Synthesis
  作者：Sara Eisler、Navjot Chahal、Robert McDonald、Rik R. Tykwinski

  DOI：10.1002/chem.200204584

  日期：2003.6.6

  conditions (hexane solution, -78 degrees C), and the seemingly high migratory aptitude of the alkynyl moiety provides for efficient rearrangement. This, in turn, allows for multiple rearrangements in a single molecule, greatly facilitating the construction of highly unsaturated substrates. This procedure is exploited for the rapid synthesis of symmetrical and unsymmetrical 1,3,5-hexatriynes, extended polyynes

  据报道，通过修饰Fritsch-Buttenberg-Wiechell（FBW）重排合成共轭多炔结构。我们的改编提供了炔烃在卡宾/类胡萝卜素中间体中的1,2-迁移，这可通过与适当的二溴-烯烃前体进行锂-卤素交换而方便地实现。这种重排在温和的条件下（己烷溶液，-78摄氏度）非常迅速地完成，炔基部分看似高的迁移能力提供了有效的重排。反过来，这允许在单个分子中进行多个重排，极大地促进了高度不饱和底物的构建。利用该方法可快速合成对称和不对称的1,3,5-己三炔，扩展的多炔和芳基多炔构建基。
• Highly Enantioselective Alkynylation of Trifluoropyruvate with Alkynylsilanes Catalyzed by the BINAP−Pd Complex: Access to α-Trifluoromethyl-Substituted Tertiary Alcohols
  作者：Kohsuke Aikawa、Yu̅ta Hioki、Koichi Mikami

  DOI：10.1021/ol102541s

  日期：2010.12.17

  A highly enantioselective alkynylation catalyzed by the dicationic (S)-BINAP−Pd complex with a variety of alkynylsilanes and trifluoropyruvate is described. The catalytic reaction is applicable to highly enantioselective addition of polyyne to trifluoropyruvate to construct α-trifluoromethyl-substituted tertiary alcohols as enantiomerically enriched forms. The alkynyl products can be converted into

  描述了由具有多种炔基硅烷和三氟丙酮酸的双价（S）-BINAP-Pd络合物催化的高度对映选择性炔基化反应。该催化反应适用于将聚炔高度对映体选择性地加成到三氟丙酮酸中，以构建对映体富集形式的α-三氟甲基取代的叔醇。炔基产物可以转化为带有三氟甲基的手性烯丙基。
• Reactions of Terminal Polyynes with Benzyl Azide
  作者：Thanh Luu、Boris J. Medos、Erin R. Graham、Danielle M. Vallee、Robert McDonald、Michael J. Ferguson、Rik R. Tykwinski

  DOI：10.1021/jo101870y

  日期：2010.12.17

  Terminal di-, tri-, tetra-, and pentaynes substituted with a variety of functional groups react with benzyl azide in the presence of CuSO4 center dot 5H(2)O and ascorbic acid to give derivatives of 4-ethynyl-, 4-butadiynyl-, 4-hexatriynyl-, and 4-octatetraynyl-,2,3-triazoles in moderate to good yields. These reactions appear to proceed regioselectively, and functionalization occurs exclusively at the terminal alkyne moiety. As well, no evidence of multiple azide additions to the polyyne framework is observed. X-ray crystallographic analysis of nine derivatives is used to document the regioselectivity of the reaction as well as outline structural characteristics of the 1,2,3-triazole products.
• Regioselective Trapping of Terminal Di-, Tri-, and Tetraynes with Benzyl Azide
  作者：Thanh Luu、Robert McDonald、Rik R. Tykwinski

  DOI：10.1021/ol062522a

  日期：2006.12.1

  The reaction of benzyl azide with terminal di-, tri-, and tetraynes appended with a range of functional groups has been explored. Standard reaction conditions for BnN3 catalyzed by CuSO(4)(.)5H(2)O gave alkynyl, butadiynyl, and hexatriynyl triazoles in moderate to good yields. The reaction proceeds regioselectively as determined by the X-ray crystallographic analysis of three derivatives (1c, 1d, and 3c), and no evidence of multiple azide addition to the polyyne framework is observed.
• Highly Efficient and Selective Synthesis of Conjugated Triynes and Higher Oligoynes of Biological and Materials Chemical Interest via Palladium-Catalyzed Alkynyl−Alkenyl Coupling
  作者：Estelle Métay、Qian Hu、Ei-ichi Negishi

  DOI：10.1021/ol0623825

  日期：2006.12.1

  Iteration of a Pd-catalyzed reaction of alkynyl- and oligoynylzincs with (E)-ICH-CHCI followed by metalation-termination with electrophiles(E) has provided a linear route to conjugated tri- and tetraynes, and Pd-catalyzed monoalkynylation of 1,1-dibromoenynes accompanied by dehydrobromination has provided a convergent route to conjugated tri-, tetra-, and pentaynes. Both display unprecedented high efficiency and selectivity.