(hepta-1,6-diyn-1-yl)tris(propan-2-yl)silane | 852385-10-5

• 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: (hepta-1,6-diyn-1-yl)tris(propan-2-yl)silane
• 英文别名: hepta-1,6-diynyl-tri(propan-2-yl)silane
• CAS: 852385-10-5
• 化学式: C₁₆H₂₈Si
• 分子量: 248.484
• InChiKey: JMSBGDREESLGQT-UHFFFAOYSA-N

物化性质

• 沸点：
  282.6±23.0 °C(Predicted)
• 密度：
  0.837±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.01
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (hepta-1,6-diyn-1-yl)tris(propan-2-yl)silane 在 tris-(dibenzylideneacetone)dipalladium(0) 、 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 、 双(2-二苯基磷苯基)醚 、 sodium t-butanolate 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 3.0h， 生成 triisopropyl(8-(tetrahydrofuran-2-yl)octa-1,6-diyn-1-yl)silane
  参考文献：
  名称：

  Pd(0)-Catalyzed Alkene Oxy- and Aminoalkynylation with Aliphatic Bromoacetylenes

  摘要：

  Tetrahydrofurans and pyrrolidines are among the most important heterocycles found in bioactive compounds. Cyclization-functionalization domino reactions of alcohols or amines onto olefins,constitute one of the most efficient methods to access them. In this context oxy- and aminoalkynylation are especially important reactions because of the numerous transformations possible with the triple bond of acetylenes yet these methods have been limited to the use of silyl protected acetylenes. Herein we report the first palladium-catalyzed oxy- and aminoalkynylation using aliphatic bromoalkynes which proceeded with high diastereoselectivity and functional group tolerance. A one-pot hydrogenation of the triple bond gave then access to alkyl-substituted tetrahydrofurans and pyrroldines. Finally a detailed study of the side products formed during the reaction gave a first insight into the reaction mechanism.

  DOI：

  10.1021/jo400254q
• 作为产物：
  描述：

  1,6-庚二炔 、 三异丙基氯硅烷 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 59.5h， 以48%的产率得到(hepta-1,6-diyn-1-yl)tris(propan-2-yl)silane
  参考文献：
  名称：

  Pd(0)-Catalyzed Alkene Oxy- and Aminoalkynylation with Aliphatic Bromoacetylenes

  摘要：

  Tetrahydrofurans and pyrrolidines are among the most important heterocycles found in bioactive compounds. Cyclization-functionalization domino reactions of alcohols or amines onto olefins,constitute one of the most efficient methods to access them. In this context oxy- and aminoalkynylation are especially important reactions because of the numerous transformations possible with the triple bond of acetylenes yet these methods have been limited to the use of silyl protected acetylenes. Herein we report the first palladium-catalyzed oxy- and aminoalkynylation using aliphatic bromoalkynes which proceeded with high diastereoselectivity and functional group tolerance. A one-pot hydrogenation of the triple bond gave then access to alkyl-substituted tetrahydrofurans and pyrroldines. Finally a detailed study of the side products formed during the reaction gave a first insight into the reaction mechanism.

  DOI：

  10.1021/jo400254q

文献信息

• Iron-Catalyzed Trimerization of Terminal Alkynes Enabled by Pyrimidinediimine Ligands: A Regioselective Method for the Synthesis of 1,3,5-Substituted Arenes
  作者：Julianna S. Doll、Robert Eichelmann、Leif E. Hertwig、Thilo Bender、Vincenz J. Kohler、Eckhard Bill、Hubert Wadepohl、Dragoş-Adrian Roşca

  DOI：10.1021/acscatal.1c00978

  日期：2021.5.7

  to a functional-group-tolerant methodology for the catalytic trimerization of terminal aliphatic alkynes. Remarkably, in contrast to established alkyne trimerization protocols, the 1,3,5-substituted arenes are the main reaction products. Preliminary mechanistic investigations suggest that the enhanced π-acidity of the pyrimidine ring, combined with the hemilability of the imine groups coordinated to

  众所周知的吡啶二亚胺（PDI）铁络合物的基于嘧啶的类似物的开发，使得能够使用功能基团耐受的方法对末端脂肪族炔烃进行催化三聚。值得注意的是，与已建立的炔三聚方案相反，1,3,5-取代的芳烃是主要的反应产物。初步的机械研究表明，嘧啶环的增强的π-酸度，与与铁中心配位的亚胺基团的半胱氨酸结合，促进了这种转变。催化循环的入口是可分离的二氮铁络合物。催化反应通过1，3-取代的金属环进行，这解释了所观察到的1，3，5-区域选择性。可以分离出这样的金属环，代表稀有的1，
• Differential Dihydrofunctionalization: A Dual Catalytic Three‐Component Coupling of Alkynes, Alkenyl Bromides, and Pinacolborane
  作者：James E. Baumann、Gojko Lalic

  DOI：10.1002/anie.202206462

  日期：2022.9.12

  differential dihydrofunctionalization of terminal alkynes enables the synthesis of allylic boronate esters through reductive three-component coupling of terminal alkynes, alkenyl bromides, and pinacolborane. The transformation is promoted by cooperative action of a copper/palladium catalyst system and results in hydrofunctionalization of both π-bonds of an alkyne.

  末端炔烃差异二氢官能化的新方法能够通过末端炔烃、烯基溴和频哪醇硼烷的还原三组分偶联合成烯丙基硼酸酯。该转化是通过铜/钯催化剂体系的协同作用促进的，并导致炔烃的两个π键的氢官能化。
• Regio- and Diastereoselective Synthesis of E-Allylic Amines through Hydroalkylation of Terminal Alkynes
  作者：Bofei Wang、Avijit Hazra、Gojko Lalic

  DOI：10.1021/acscatal.4c00853

  日期：2024.4.19

  Allylic amines make up an important class of organic compounds that have inspired the development of numerous methods for their synthesis. One of the most effective transformations involves the coupling of internal alkynes with appropriate nitrogen-containing electrophiles in the presence of a transition metal catalyst. We have developed a method that allows transformation of terminal alkynes into

  烯丙胺是一类重要的有机化合物，激发了许多合成方法的发展。最有效的转化之一涉及内部炔烃与适当的含氮亲电子试剂在过渡金属催化剂存在下的偶联。我们开发了一种方法，通过铜催化的还原交叉偶联与α-氯代邻苯二甲酰亚胺，将末端炔烃转化为烯丙胺。该方法具有广泛的底物范围，并导致抗马尔可夫尼科夫氢胺化产物的E异构体的高选择性形成。初步的机理研究支持涉及炔烃氢化和溶剂笼自由基对形成的机制。