(4E,8E)-4,8-Dimethyl-14-trimethylsilanyl-tetradeca-4,8-dien-12-ynal | 210584-22-8

• 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: (4E,8E)-4,8-Dimethyl-14-trimethylsilanyl-tetradeca-4,8-dien-12-ynal
• 英文别名: (4E,8E)-4,8-dimethyl-14-trimethylsilyltetradeca-4,8-dien-12-ynal
• CAS: 210584-22-8
• 化学式: C₁₉H₃₂OSi
• 分子量: 304.548
• InChiKey: VJWIUVUWTGPWFZ-IJNKXORISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.76
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  diphenylisopropylsulfonium tetrafluoroborate 、 (4E,8E)-4,8-Dimethyl-14-trimethylsilanyl-tetradeca-4,8-dien-12-ynal 在 叔丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以91%的产率得到[(6E,10E)-13-(3,3-Dimethyl-oxiranyl)-7,11-dimethyl-trideca-6,10-dien-2-ynyl]-trimethyl-silane
  参考文献：
  名称：

  Tricyclization of an Epoxypolyene Utilizing Zeolites as Next-Generation Biomimetic Cyclization Promoters:  Evidence of Surface and Pore Selectivity in the Cyclization Process

  摘要：

  A new approach for the biomimetic polyene cyclization of epoxyolefins is demonstrated by the zeolite-promoted tricyclization of 1. Reaction of 1 with a variety of zeolitic materials, including Zeolite A, Mordenite, Faujasite, and ZSM-5, yielded variable amounts of cyclic and acyclic epoxide-rearranged materials. Small-pore Zeolite A, in either the Na or Li form, caused the exclusive formation of ketone 3, while both H-Mordenite and H-ZSM-5 were sufficiently reactive to provide tricyclic products in modest yields. Low recovery of polyene 1 was observed when larger-pore zeolites of type Beta and H-Faujasite were utilized as cyclization promoters, suggesting that decomposition products had been included within the zeolite cavity. Dramatic improvement in reaction selectivity was achieved after surface dealumination of H-ZSM-5, which gave 52% (isolated yield) of tricycle 2. Compared to the Lewis acid cyclization of 1 by Ti(OiPr)Cl-3 or MeAlCl2, the reaction is highly stereoselective, producing the all-trans tricycle as the predominant product. These results, in conjunction with surface and pore deactivation studies using pyridine bases, suggest that the cyclization is initiated at the opening of the zeolite pores, with concurrent adsorption of the polyene onto the aluminosilicate surface.

  DOI：

  10.1021/jo980318y
• 作为产物：
  描述：

  (E)-2,6-Dimethyl-12-trimethylsilanyl-dodeca-1,6-dien-10-yn-3-ol 在 二异丁基氢化铝 、 丙酸 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.0h， 生成 (4E,8E)-4,8-Dimethyl-14-trimethylsilanyl-tetradeca-4,8-dien-12-ynal
  参考文献：
  名称：

  Tricyclization of an Epoxypolyene Utilizing Zeolites as Next-Generation Biomimetic Cyclization Promoters:  Evidence of Surface and Pore Selectivity in the Cyclization Process

  摘要：

  A new approach for the biomimetic polyene cyclization of epoxyolefins is demonstrated by the zeolite-promoted tricyclization of 1. Reaction of 1 with a variety of zeolitic materials, including Zeolite A, Mordenite, Faujasite, and ZSM-5, yielded variable amounts of cyclic and acyclic epoxide-rearranged materials. Small-pore Zeolite A, in either the Na or Li form, caused the exclusive formation of ketone 3, while both H-Mordenite and H-ZSM-5 were sufficiently reactive to provide tricyclic products in modest yields. Low recovery of polyene 1 was observed when larger-pore zeolites of type Beta and H-Faujasite were utilized as cyclization promoters, suggesting that decomposition products had been included within the zeolite cavity. Dramatic improvement in reaction selectivity was achieved after surface dealumination of H-ZSM-5, which gave 52% (isolated yield) of tricycle 2. Compared to the Lewis acid cyclization of 1 by Ti(OiPr)Cl-3 or MeAlCl2, the reaction is highly stereoselective, producing the all-trans tricycle as the predominant product. These results, in conjunction with surface and pore deactivation studies using pyridine bases, suggest that the cyclization is initiated at the opening of the zeolite pores, with concurrent adsorption of the polyene onto the aluminosilicate surface.

  DOI：

  10.1021/jo980318y