tert-butyldimethyl((6-(trimethylsilyl)hexa-3,5-diyn-1-yl)oxy)silane | 1452808-12-6

• 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: tert-butyldimethyl((6-(trimethylsilyl)hexa-3,5-diyn-1-yl)oxy)silane
• 英文别名: Tert-butyl-dimethyl-(6-trimethylsilylhexa-3,5-diynoxy)silane；tert-butyl-dimethyl-(6-trimethylsilylhexa-3,5-diynoxy)silane
• CAS: 1452808-12-6
• 化学式: C₁₅H₂₈OSi₂
• 分子量: 280.558
• InChiKey: VXJSBGIAXCZHSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyldimethyl((6-(trimethylsilyl)hexa-3,5-diyn-1-yl)oxy)silane 在 C₂₈H₃₁N₃O 、 cobalt acetylacetonate 作用下， 以 四氢呋喃 为溶剂， 反应 66.0h， 生成
  参考文献：
  名称：

  Cobalt-Catalyzed Regiodivergent Stereoselective Hydroboration of 1,3-Diynes To Access Boryl-Functionalized Enynes

  摘要：

  We report a regiodivergent and stereoselective hydroboration of 1,3-diynes with pinacolborane (HBpin) in the presence of cobalt catalysts generated in situ from bench-stable Co(acac)(2) and bisphosphine ligands. These cobalt catalysts were activated by the reactions with HBpin. A range of unsymmetrical and symmetrical 1,3-diynes reacted smoothly with HBpin in the presence of Co(acac)(2)/xantphos to selectively afford enynylboronate products with boron addition to the internal carbon of the 1,3-diyne unit. However, these 1,3-diynes reacted in the presence of Co(acac)(2)/dppf to form enynylboronate products with boron addition to the external carbon of the 1,3-diyne unit. These hydroboration reactions show good functional group compatibility and can be readily scaled up to gram-scales without using a drybox. Deuterium-labeling experiments suggest a cis-addition of HBpin to the less-hindered triple bond of 1,3-diynes. Furthermore, the comparison of the regioselectivity between cobalt-catalyzed hydrosilylation and hydroboration reactions of the same 1,3-diyne substrate suggests that Co(acac)(2)/xantphos-catalyzed regioselective 1,3-diyne hydroboration proceeds through a cobalt-hydride intermediate while Co(acac)(2)/dppf-catalyzed 1,3-diyne hydroboration proceed through a cobalt boryl intermediate.

  DOI：

  10.1021/acscatal.9b03139
• 作为产物：
  描述：

  6-(trimethylsilyl)hexa-3,5-diyn-1-ol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以86%的产率得到tert-butyldimethyl((6-(trimethylsilyl)hexa-3,5-diyn-1-yl)oxy)silane
  参考文献：
  名称：

  Kingianins A，D和F的全合成

  摘要：

  适合国王的合成：（±）-kingianins A，D和F的总合成已通过十个步骤完成。主要特性包括克级合成和到（部分还原的共轭tetrayne的Ž，Ž，Ž，Ž）-tetraene，一个（的多米诺8π-6π电环环闭合Ž，Ž，Ž，Ž）-tetraene ，以及功能化的双环[4.2.0]辛二烯前体的自由基阳离子催化形式Diels-Alder二聚。

  DOI：

  10.1002/anie.201210084

文献信息

• Radical <i>trans</i>-Hydroboration of Substituted 1,3-Diynes with an <i>N</i>-Heterocyclic Carbene Borane
  作者：Kosuke Takahashi、Steven J. Geib、Katsuhiro Maeda、Dennis P. Curran、Tsuyoshi Taniguchi

  DOI：10.1021/acs.orglett.0c04284

  日期：2021.2.5

  Monohydroboration of substituted 1,3-diynes with an N-heterocyclic carbene borane (NHC–borane) occurs under radical conditions using an azo initiator, such as ACCN and AIBN, and a thiol as a polarity-reversal catalyst. The reaction is highly regio- and stereoselective and provides stable NHC-(E)-alkynylalkenylboranes.

  在自由基条件下，使用偶氮引发剂（如ACCN和AIBN）和硫醇作为极性反转催化剂，可将N-杂环卡宾硼烷（NHC-硼烷）取代的1,3-二炔单氢硼化。该反应是高度区域和立体选择性的，并提供稳定的NHC-（E）-炔基烯基硼烷。
• Cobalt-Catalyzed Regiodivergent Stereoselective Hydroboration of 1,3-Diynes To Access Boryl-Functionalized Enynes
  作者：Hui Leng Sang、Caizhi Wu、Guan Ge Darren Phua、Shaozhong Ge

  DOI：10.1021/acscatal.9b03139

  日期：2019.11.1

  We report a regiodivergent and stereoselective hydroboration of 1,3-diynes with pinacolborane (HBpin) in the presence of cobalt catalysts generated in situ from bench-stable Co(acac)(2) and bisphosphine ligands. These cobalt catalysts were activated by the reactions with HBpin. A range of unsymmetrical and symmetrical 1,3-diynes reacted smoothly with HBpin in the presence of Co(acac)(2)/xantphos to selectively afford enynylboronate products with boron addition to the internal carbon of the 1,3-diyne unit. However, these 1,3-diynes reacted in the presence of Co(acac)(2)/dppf to form enynylboronate products with boron addition to the external carbon of the 1,3-diyne unit. These hydroboration reactions show good functional group compatibility and can be readily scaled up to gram-scales without using a drybox. Deuterium-labeling experiments suggest a cis-addition of HBpin to the less-hindered triple bond of 1,3-diynes. Furthermore, the comparison of the regioselectivity between cobalt-catalyzed hydrosilylation and hydroboration reactions of the same 1,3-diyne substrate suggests that Co(acac)(2)/xantphos-catalyzed regioselective 1,3-diyne hydroboration proceeds through a cobalt-hydride intermediate while Co(acac)(2)/dppf-catalyzed 1,3-diyne hydroboration proceed through a cobalt boryl intermediate.
• Total Synthesis of Kingianins A, D, and F
  作者：Samuel L. Drew、Andrew L. Lawrence、Michael S. Sherburn

  DOI：10.1002/anie.201210084

  日期：2013.4.8

  A synthesis fit for a king: The total synthesis of (±)‐kingianins A, D, and F has been achieved in ten steps. Key features include the gram‐scale synthesis and partial reduction of a conjugated tetrayne to a (Z,Z,Z,Z)‐tetraene, the domino 8π–6π electrocyclic ring closure of a (Z,Z,Z,Z)‐tetraene, and the radical‐cation‐catalyzed formal Diels–Alder dimerization of functionalized bicyclo[4.2.0]octadiene

  适合国王的合成：（±）-kingianins A，D和F的总合成已通过十个步骤完成。主要特性包括克级合成和到（部分还原的共轭tetrayne的Ž，Ž，Ž，Ž）-tetraene，一个（的多米诺8π-6π电环环闭合Ž，Ž，Ž，Ž）-tetraene ，以及功能化的双环[4.2.0]辛二烯前体的自由基阳离子催化形式Diels-Alder二聚。