((1-bromonon-1-yn-3-yl)oxy)triisopropylsilane | 1427729-40-5

• 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-bromonon-1-yn-3-yl)oxy)triisopropylsilane
• 英文别名: 1-Bromonon-1-yn-3-yloxy-tri(propan-2-yl)silane；1-bromonon-1-yn-3-yloxy-tri(propan-2-yl)silane
• CAS: 1427729-40-5
• 化学式: C₁₈H₃₅BrOSi
• 分子量: 375.465
• InChiKey: PFASWODHXQMHSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.87
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  4-戊烯-1-醇 、 ((1-bromonon-1-yn-3-yl)oxy)triisopropylsilane 在 tris-(dibenzylideneacetone)dipalladium(0) 、 双(2-二苯基磷苯基)醚 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以78%的产率得到triisopropyl((1-(tetrahydrofuran-2-yl)dec-2-yn-4-yl)oxy)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：

  non-1-yn-3-ol 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 ((1-bromonon-1-yn-3-yl)oxy)triisopropylsilane
  参考文献：
  名称：

  使用三氟乙醛衍生的系链，钯催化烯丙醇的氨基甲酸酯化

  摘要：

  据报道，基于易引入的三氟乙醛衍生的系链的使用，钯的烯丙基醇的碳氨化反应被报道。使用炔基溴化物和可商购的膦配体实现氨基炔基化反应。对于氨基芳基化，引入了新的联芳基膦配体“ Fu-XPhos”，以克服竞争性的Heck途径。碳氨化产物以高收率和非对映选择性获得。可以轻松移除系链，以提供增值的氨基醇结构单元。

  DOI：

  10.1021/acs.orglett.7b01524

文献信息

• One-Pot Three-Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination
  作者：Ugo Orcel、Jerome Waser

  DOI：10.1002/anie.201607318

  日期：2016.10.4

  A synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron‐poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium‐catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl

  据报道，邻位二胺通过原位氨基形成和烯丙基胺的碳氨化而合成。采用稳定的血红素形式的高度贫电子的三氟甲基亚胺是实现快速，完整的氨基形成以及钯催化的碳氨化步骤的关键。所开发的条件允许引入具有完全区域选择性和高非对映选择性的各种炔基，乙烯基，芳基和杂芳基。该反应表现出较高的官能团耐受性。重要的是，咪唑烷产物中的任何一个氮原子都可以被选择性地脱保护，而在温和的条件下一步一步去除氨基链则可以显示出游离的二胺。我们希望这项工作将促进在有机合成中进一步使用混合的氨基系链。
• Pd(0)-Catalyzed Alkene Oxy- and Aminoalkynylation with Aliphatic Bromoacetylenes
  作者：Stefano Nicolai、Raha Sedigh-Zadeh、Jérôme Waser

  DOI：10.1021/jo400254q

  日期：2013.4.19

  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.
• Palladium-Catalyzed Carboamination of Allylic Alcohols Using a Trifluoroacetaldehyde-Derived Tether
  作者：Bastian Muriel、Ugo Orcel、Jerome Waser

  DOI：10.1021/acs.orglett.7b01524

  日期：2017.7.7

  selective palladium-catalyzed carboamination of allylic alcohols is reported on the basis of the use of an easily introduced trifluoroacetaldehyde-derived tether. Aminoalkynylation reactions were realized using alkynyl bromides and commercially available phosphine ligands. For aminoarylations, a new biaryl phosphine ligand, “Fu-XPhos”, was introduced to overcome a competitive Heck pathway. The carboamination

  据报道，基于易引入的三氟乙醛衍生的系链的使用，钯的烯丙基醇的碳氨化反应被报道。使用炔基溴化物和可商购的膦配体实现氨基炔基化反应。对于氨基芳基化，引入了新的联芳基膦配体“ Fu-XPhos”，以克服竞争性的Heck途径。碳氨化产物以高收率和非对映选择性获得。可以轻松移除系链，以提供增值的氨基醇结构单元。