methyl (Z)-7-methyl-3-(trimethylsilyl)methyl-2,6-octadienoate | 81752-85-4

• 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: methyl (Z)-7-methyl-3-(trimethylsilyl)methyl-2,6-octadienoate
• 英文别名: methyl (Z)-7-methyl-3-((trimethylsilyl)methyl)octa-2,6-dienoate；methyl (2Z)-7-methyl-3-(trimethylsilylmethyl)octa-2,6-dienoate
• CAS: 81752-85-4
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: DTKIKDKKJOEZHB-RAXLEYEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (Z)-7-methyl-3-(trimethylsilyl)methyl-2,6-octadienoate 在 potassium osmate(VI) 、 甲基磺酰胺 lithium aluminium tetrahydride 、 (DHQD)2PHAL 、 三氟化硼乙醚 、 potassium carbonate 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 33.5h， 生成 (1RS,3SR)-3-(hydroxymethyl)-2,2-dimethyl-4-methylenecyclohexanol
  参考文献：
  名称：

  Enantioselective synthesis of both enantiomers of γ-ionone, γ-damascone, karahana lactone and karahana ether

  摘要：

  A straightforward enantioselective synthesis of both enantiomers of the title compounds is described starting from enantiopure methyl (2S,6R)- or (2R,6S)-cis-2-hydroxy-gamma-cyclogeraniate. These versatile building blocks are obtained by biomimetic cyclization of methyl (6S)- or (6R)-(Z)-6,7-epoxy-7-methyl-3-(trimethylsilyl)methyl-2-octenoate, respectively. The chiral information was encoded by a highly regioselective Sharpless asymmetric dihydroxylation of the corresponding diene. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00335-x
• 作为产物：
  描述：

  methyl 7-methyl-3-oxooct-6-enoate 在 bis(acetylacetonate)nickel(II) sodium hydride 作用下， 生成 methyl (Z)-7-methyl-3-(trimethylsilyl)methyl-2,6-octadienoate
  参考文献：
  名称：

  Electrophilic cyclization of polyene allylsilanes. Synthesis of albicanyl acetate

  摘要：

  联烯基硅烷5 [化学式：见文本] 是通过镍（II）催化的甲基三硅基甲烷镁和相应的β-酮酯的烯醇磷酸酯偶联制备的。氯化锡和三氟乙酸汞促进了5的环化反应。从5b得到的产物被转化成海洋天然产物阿尔比卡尼酯（1）[化学式：见文本]。

  DOI：

  10.1139/v82-098

文献信息

• Use of a Lithiolactone in the Enantioselective Constructions of A/C seco-B and of A/B seco-C proTaxol Systems
  作者：Gilbert Stork、Takayuki Doi、Longbin Liu

  DOI：10.1016/s0040-4039(97)01793-0

  日期：1997.10

  We show that an unusual lithiolactone system is a useful starting point for the construction of various intermediates to the taxol structure. © 1997 Elsevier Science Ltd.

  我们表明，一个不寻常的硫代内酯体系是构建紫杉醇结构各种中间体的有用起点。©1997爱思唯尔科学有限公司。
• A concise synthesis approach to optically active taxol C-ring fragment
  作者：Masahisa Nakada、Ei-ichi Kojima、Yukitaka Iwata

  DOI：10.1016/s0040-4039(97)10554-8

  日期：1998.1

  A concise synthetic approach to an optically active taxol C-ring fragment starting from a readily available compound is described. Lewis acid promoted-cyclization of optically active epoxy trimethylsilane 7 affords the key intermediate 8 in 69% yield (at 91% conversion). Further transformation of 8 to our taxol C-ring fragment is successfully achieved in a stereoselective manner.

  描述了从容易获得的化合物开始的光学活性紫杉醇C-环片段的简明合成方法。路易斯酸促进的光学活性环氧三甲基硅烷7的环化反应以69％的收率（91％的转化率）提供了关键中间体8。以立体选择性的方式成功实现了8到我们的紫杉醇C环片段的进一步转化。
• Armstrong, Rosemary J.; Weiler, Larry, Canadian Journal of Chemistry, 1983, vol. 61, p. 2530 - 2539
  作者：Armstrong, Rosemary J.、Weiler, Larry

  DOI：——

  日期：——
• Synthesis of Two Key Fragments of the Complex Polyhalogenated Marine Meroterpenoid Azamerone
  作者：Simon D. Schnell、Anthony Linden、Karl Gademann

  DOI：10.1021/acs.orglett.9b00090

  日期：2019.2.15

  A concise route toward two advanced fragments in the context of the total synthesis of the unique natural product azamerone is reported. Key synthetic features include the enantioselective synthesis of an epoxysilane and its Lewis-acid-induced cyclization and the installation of the pyridazine ring via a formylation/condensation sequence. This route provides strategic insights into the chemistry of phthalazinediols, facilitating synthetic approaches toward this class of natural products.
• TiF4-mediated biomimetic alkylation–cyclization cascade reaction of 2-trimethylsilylmethyl-1,5-dienes with aldehydes
  作者：Luigi Anastasia、Elios Giannini、Giuseppe Zanoni、Giovanni Vidari

  DOI：10.1016/j.tetlet.2005.06.149

  日期：2005.8

  TiF4 has proven to be the Lewis acid of choice for promoting the biomimetic addition of 2-trimethylsilylmethyl-1,5-dienes to aliphatic aldehydes with concomitant cyclization. 1,3-cis-Disubstituted methylenecyclohexanes are thus produced in good yields and high diastereoselectivity. The reaction appears to proceed via a highly concerted mechanism involving a chair-like transition state. (c) 2005 Elsevier Ltd. All rights reserved.