(E,E)-CH2CHCH2CH2C(CH3)CHCH2CH2C(CH3)CHCH(CH3)CH2OH | 1006047-94-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (E,E)-CH2CHCH2CH2C(CH3)CHCH2CH2C(CH3)CHCH(CH3)CH2OH
• 英文别名: (3E,7E)-2,4,8-trimethyldodeca-3,7,11-trien-1-ol
• CAS: 1006047-94-4
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: LLMRQHRUUAXCQZ-IJFRVEDASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E,E)-CH2CHCH2CH2C(CH3)CHCH2CH2C(CH3)CHCH(CH3)CH2OH 、 [PtI(PhP(CH2CH2PPh2)2)]I 在 silver tetrafluoroborate 作用下， 以 not given 为溶剂， 生成 [PtMe(PhP(CH2CH2PPh2)2)((CH3)3C12H16O)](1+)
  参考文献：
  名称：

  Reversibility Effects on the Stereoselectivity of Pt(II)-Mediated Cascade Poly-ene Cyclizations

  摘要：

  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.

  DOI：

  10.1021/ja075518i

文献信息

• 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.