[(6E,10E)-13-(3,3-Dimethyl-oxiranyl)-7,11-dimethyl-trideca-6,10-dien-2-ynyl]-trimethyl-silane | 143306-70-1

• 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: [(6E,10E)-13-(3,3-Dimethyl-oxiranyl)-7,11-dimethyl-trideca-6,10-dien-2-ynyl]-trimethyl-silane
• 英文别名: [(6E,10E)-13-(3,3-dimethyloxiran-2-yl)-7,11-dimethyltrideca-6,10-dien-2-ynyl]-trimethylsilane
• CAS: 143306-70-1
• 化学式: C₂₂H₃₈OSi
• 分子量: 346.629
• InChiKey: MGFFWIYOPVFBAW-YLYRKCBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.74
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [(6E,10E)-13-(3,3-Dimethyl-oxiranyl)-7,11-dimethyl-trideca-6,10-dien-2-ynyl]-trimethyl-silane 在 Ti(OiPr)Cl3 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以12%的产率得到(3aS,5aR,7S,9aR,9bS)-3a,6,6,9a-Tetramethyl-3-vinylidene-dodecahydro-cyclopenta[a]naphthalen-7-ol
  参考文献：
  名称：

  Epoxide-initiated cationic polyene cyclisations

  摘要：

  The Lewis acid (2-propoxy)titanium trichloride is an efficient reagent for epoxide-initiated polyene cyclisations. Thus, 4 underwent tricyclisation to yield tricyclic products 5-7 in 73 % yield. The tetraene epoxide 1 gave pentacycle 15 in 21 % yield. The latter is the first example of a cationic pentacarbocyclisalion.

  DOI：

  10.1016/s0040-4039(00)61492-2
• 作为产物：
  描述：

  (E)-4-methyl-10-trimethylsilyldec-4-en-8-ynal 在 叔丁基锂 、 二异丁基氢化铝 、 丙酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 6.0h， 生成 [(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

文献信息

• Ferric chloride, an efficient promoter of cationic polyene cyclizations
  作者：Stephanie E. Sen、Steven L. Roach、Sarah M. Smith、Yan zhi Zhang

  DOI：10.1016/s0040-4039(98)00738-2

  日期：1998.6

  The ability of ferric chloride to function as a promoter in biomimetic polyene cyclizations was evaluated using epoxy-polyene 1 as substrate. Reaction of 1 with either FeCl3·6H2O or anhydrous FeCl3 yielded tricyclic alcohols 2a-c in excellent yield, with comparable efficiency to MeAlCl2 and Ti(i-OPr)Cl3. This method can be extended to the cyclization of other polyene substrates, as seen in the conversion

  使用环氧多烯1作为底物评估氯化铁在仿生多烯环化中用作促进剂的能力。的反应1与任一的FeCl 3 ·6H 2 O或无水的FeCl 3，得到三环醇2a-c中的优良率，具有相当的效率，以MeAlCl 2和Ti（我-OPr）氯3。该方法可以扩展到其他多烯底物的环化反应，如将7转化为十氢化萘衍生物8所示。
• Epoxide-initiated cationic polyene cyclisations
  作者：Paul V. Fish、Anantha R. Sudhakar、William S. Johnson

  DOI：10.1016/s0040-4039(00)61492-2

  日期：1993.12

  The Lewis acid (2-propoxy)titanium trichloride is an efficient reagent for epoxide-initiated polyene cyclisations. Thus, 4 underwent tricyclisation to yield tricyclic products 5-7 in 73 % yield. The tetraene epoxide 1 gave pentacycle 15 in 21 % yield. The latter is the first example of a cationic pentacarbocyclisalion.
• 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.