(E)-2,6-Dimethyl-12-trimethylsilanyl-dodeca-1,6-dien-10-yn-3-ol | 143306-76-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2,6-Dimethyl-12-trimethylsilanyl-dodeca-1,6-dien-10-yn-3-ol
• 英文别名: (6E)-2,6-dimethyl-12-trimethylsilyldodeca-1,6-dien-10-yn-3-ol
• CAS: 143306-76-7
• 化学式: C₁₇H₃₀OSi
• 分子量: 278.51
• InChiKey: UFBARBRZPFYGCU-LFIBNONCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.65
• 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)-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
• 作为产物：
  描述：

  (E)-4-methyl-10-trimethylsilyldec-4-en-8-ynal 在 4 A molecular sieve 、 叔丁基锂 作用下， 以 苯 为溶剂， 反应 7.0h， 生成 (E)-2,6-Dimethyl-12-trimethylsilanyl-dodeca-1,6-dien-10-yn-3-ol
  参考文献：
  名称：

  Zeolite-Mediated Cyclization of an Epoxide-Containing Polyene

  摘要：

  The utility of zeolites as promoters for the cyclization of an epoxide-containing polyene has been investigated. Reaction of polyene 1 with oven-dried 4 Angstrom molecular sieves (type A zeolite) proceeds efficiently to generate bicyclic alcohol 2 in a 90% isolated yield. The reaction is sensitive to a variety of factors, including solvent type, water content, and zeolite acidity. Reactivity is apparently due to the zeolite lattice, since alumina and silica either are unreactive or generate a complex mixture of epoxide ring-opened products. Compared to the aluminum-based Lewis acid Me(2)AlCl, the zeolite-promoted cyclization of 1 was a more facile reaction, providing excellent product recovery after filtration. These results indicate that zeolites represent a new class of promoters in biomimetic polyene cyclizations.

  DOI：

  10.1021/jo960745g

文献信息

• Tricyclization of an Epoxypolyene Utilizing Zeolites as Next-Generation Biomimetic Cyclization Promoters:  Evidence of Surface and Pore Selectivity in the Cyclization Process
  作者：Stephanie E. Sen、Yan zhi Zhang、Sarah M. Smith、John C. Huffman

  DOI：10.1021/jo980318y

  日期：1998.6.1

  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.
• Zeolite-Mediated Cyclization of an Epoxide-Containing Polyene
  作者：Stephanie E. Sen、Yan zhi Zhang、Steven L. Roach

  DOI：10.1021/jo960745g

  日期：1996.1.1

  The utility of zeolites as promoters for the cyclization of an epoxide-containing polyene has been investigated. Reaction of polyene 1 with oven-dried 4 Angstrom molecular sieves (type A zeolite) proceeds efficiently to generate bicyclic alcohol 2 in a 90% isolated yield. The reaction is sensitive to a variety of factors, including solvent type, water content, and zeolite acidity. Reactivity is apparently due to the zeolite lattice, since alumina and silica either are unreactive or generate a complex mixture of epoxide ring-opened products. Compared to the aluminum-based Lewis acid Me(2)AlCl, the zeolite-promoted cyclization of 1 was a more facile reaction, providing excellent product recovery after filtration. These results indicate that zeolites represent a new class of promoters in biomimetic polyene cyclizations.