8-iodo-5-methyl-1,5-octadiene | 757960-33-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 英文名称: 8-iodo-5-methyl-1,5-octadiene
• 英文别名: (5E)-8-iodo-5-methylocta-1,5-diene
• CAS: 757960-33-1
• 化学式: C₉H₁₅I
• 分子量: 250.123
• InChiKey: ZSEBEBUAPUYTHW-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  8-iodo-5-methyl-1,5-octadiene 在 二(氰基苯)二氯化钯 对苯醌 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 50.0h， 生成 (3aR,7aR)-7a-Methyl-1-(toluene-4-sulfonyl)-octahydro-indole
  参考文献：
  名称：

  Pd（II）催化的碳正离子环化：在氧化条件下的后续重排和捕集

  摘要：

  据报道，由1,5-二烯与Pd（II）的碳环化引发的催化氧化多环化反应。用合适的官能团（苯酚，烯烃，醇，磺酰胺）或重排方案（Pinacol）捕获假定的碳阳离子可得到高收率和出色的非对映选择性的多环产物。中间Pd–C键的周转是通过β-H消除。

  DOI：

  10.1016/j.tet.2004.06.023
• 作为产物：
  描述：

  (E)-4-Methyl-octa-3,7-dien-1-ol 在 三乙胺 、 sodium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 8-iodo-5-methyl-1,5-octadiene
  参考文献：
  名称：

  Pd（II）催化的碳正离子环化：在氧化条件下的后续重排和捕集

  摘要：

  据报道，由1,5-二烯与Pd（II）的碳环化引发的催化氧化多环化反应。用合适的官能团（苯酚，烯烃，醇，磺酰胺）或重排方案（Pinacol）捕获假定的碳阳离子可得到高收率和出色的非对映选择性的多环产物。中间Pd–C键的周转是通过β-H消除。

  DOI：

  10.1016/j.tet.2004.06.023

文献信息

• Regioselective Oxidative Cation-Olefin Cyclization of Poly-enes:  Catalyst Turnover via Hydride Abstraction
  作者：Charles A. Mullen、Michel R. Gagné

  DOI：10.1021/ja073573l

  日期：2007.10.1

  Electrophilic P2Pt2+ complexes are shown to catalyze the regio- and diastereoselective oxidative cascade cyclization of poly-enes. The reactions are stereospecific with respect to the initiating alkenes geometry and suggest an all-chair, semiconcerted transition structure. Catalyst turnover after cyclization apparently occurs via beta-hydride elimination and subsequent hydride abstraction (from P2Pt-H+) by added Trityl cation (in the form of trityl methyl ether or a resin version thereof) to regenerate the active P(2)pt(2+) state. One intriguing possibility is that the high regioselectivity observed in the beta-H elimination is due to a regio-defining beta-agostic resting state.
• Reversibility Effects on the Stereoselectivity of Pt(II)-Mediated Cascade Poly-ene Cyclizations
  作者：Jeremiah A. Feducia、Michel R. Gagné

  DOI：10.1021/ja075518i

  日期：2008.1.1

  Cyclization of 1,5-dienes bearing nucleophilic traps with electrophilic trisphosphine pincer ligated Pt(II) complexes results in the formation of a polycyclic Pt-alkyl via a pt(n(2)-alkene) intermediate. With electron-rich triphosphine ligands, an equilibrium between the pt(n(2)-alkene) and Pt-alkyl was observed. The position of the equilibrium was sensitive to ligand basicity, conjugate acid strength, solvent polarity, and ring size. In cases where the ligand was electron poor and did not promote retrocyclization, the kinetic products adhering to the Stork-Eschenmoser postulate were observed (E-alkenes give trans-ring junctions). When retrocyclization was rapid, alternative thermodynamic products resulting from multistep rearrangements were observed (cis-[6,5]-bicycles). Under both kinetic and thermodynamic conditions, remote methyl substituents led to highly diastereoselective reactions. In the case of trienol substrates, long-range asymmetric induction from a C-ring substituent was considerably attenuated and only modest diastereoselectivity was observed (similar to 2:1). The data suggest that for a tricyclization, the long-range stereocontrol results from diastereo-selecting interactions that develop during the organization of the nascent rings. In contrast, the bicyclization diastereoselectivities result from reversible cascade cyclization.