1-[3-[Tert-butyl(dimethyl)silyl]oxypyrrolidin-1-yl]-2,2-dimethylbut-3-en-1-one | 724433-88-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 1-[3-[Tert-butyl(dimethyl)silyl]oxypyrrolidin-1-yl]-2,2-dimethylbut-3-en-1-one
• CAS: 724433-88-9
• 化学式: C₁₆H₃₁NO₂Si
• 分子量: 297.513
• InChiKey: RAQCEBMFOJROLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-[3-[Tert-butyl(dimethyl)silyl]oxypyrrolidin-1-yl]-2,2-dimethylbut-3-en-1-one 在 chlorobis(cyclooctene)-iridium(I) dimer 、 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene 作用下， 以 环己烷 为溶剂， 以60%的产率得到6-[tert-butyl(dimethyl)silyl]oxy-1,2,2-trimethyl-6,7-dihydro-5H-pyrrolizin-3-one
  参考文献：
  名称：

  Cross-Coupling of sp³ C−H Bonds and Alkenes:  Catalytic Cyclization of Alkene−Amide Substrates

  摘要：

  We herein present a new oxidative cyclization of alkene-amide substrates under neutral and catalytic conditions. This overall transformation requires tandem sp3 C-H activation (at the position adjacent to the amide nitrogen) and C-C bond formation. Specifically, pyrrolidine 1 was converted to pyrrolizidinone 3 and indolizidinone 4 in 66% and 17% yield, respectively, in the presence of [Ir(coe)2Cl]2, the carbene ligand IPr (1:1 metal/ligand ratio, 5-10 mol % of Ir), and the hydrogen acceptor (NBE or TBE, 3-10 equiv). The results presented in this study suggest that complex 10 [IPr-Ir(Cl)(substrate)] is the key intermediate in the catalytic cycle. On the mechanistic front, the key advance was the ability to facilitate C-H activation and alkene insertion in tandem, and in preference to beta-hydride elimination, in the context of amide substrates. With respect to complex synthesis, catalytic and neutral conditions of this method unlock new exciting opportunities as illustrated by regioselective cyclization of the proline-derived substrate 16.

  DOI：

  10.1021/ja049111e
• 作为产物：
  描述：

  2,2-二甲基-3-丁烯酸 在 咪唑 、 benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate 、 1-羟基苯并三唑 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 1-[3-[Tert-butyl(dimethyl)silyl]oxypyrrolidin-1-yl]-2,2-dimethylbut-3-en-1-one
  参考文献：
  名称：

  Cross-Coupling of sp³ C−H Bonds and Alkenes:  Catalytic Cyclization of Alkene−Amide Substrates

  摘要：

  We herein present a new oxidative cyclization of alkene-amide substrates under neutral and catalytic conditions. This overall transformation requires tandem sp3 C-H activation (at the position adjacent to the amide nitrogen) and C-C bond formation. Specifically, pyrrolidine 1 was converted to pyrrolizidinone 3 and indolizidinone 4 in 66% and 17% yield, respectively, in the presence of [Ir(coe)2Cl]2, the carbene ligand IPr (1:1 metal/ligand ratio, 5-10 mol % of Ir), and the hydrogen acceptor (NBE or TBE, 3-10 equiv). The results presented in this study suggest that complex 10 [IPr-Ir(Cl)(substrate)] is the key intermediate in the catalytic cycle. On the mechanistic front, the key advance was the ability to facilitate C-H activation and alkene insertion in tandem, and in preference to beta-hydride elimination, in the context of amide substrates. With respect to complex synthesis, catalytic and neutral conditions of this method unlock new exciting opportunities as illustrated by regioselective cyclization of the proline-derived substrate 16.

  DOI：

  10.1021/ja049111e

文献信息

• Cross-Coupling of sp³ C−H Bonds and Alkenes:  Catalytic Cyclization of Alkene−Amide Substrates
  作者：Brenton DeBoef、Stefan J. Pastine、Dalibor Sames

  DOI：10.1021/ja049111e

  日期：2004.6.1

  We herein present a new oxidative cyclization of alkene-amide substrates under neutral and catalytic conditions. This overall transformation requires tandem sp3 C-H activation (at the position adjacent to the amide nitrogen) and C-C bond formation. Specifically, pyrrolidine 1 was converted to pyrrolizidinone 3 and indolizidinone 4 in 66% and 17% yield, respectively, in the presence of [Ir(coe)2Cl]2, the carbene ligand IPr (1:1 metal/ligand ratio, 5-10 mol % of Ir), and the hydrogen acceptor (NBE or TBE, 3-10 equiv). The results presented in this study suggest that complex 10 [IPr-Ir(Cl)(substrate)] is the key intermediate in the catalytic cycle. On the mechanistic front, the key advance was the ability to facilitate C-H activation and alkene insertion in tandem, and in preference to beta-hydride elimination, in the context of amide substrates. With respect to complex synthesis, catalytic and neutral conditions of this method unlock new exciting opportunities as illustrated by regioselective cyclization of the proline-derived substrate 16.