2-trimethylsilyloxyocta-2,7-diene | 118235-30-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-trimethylsilyloxyocta-2,7-diene
• 英文别名: trimethyl(octa-2,7-dien-2-yloxy)silane
• CAS: 118235-30-6
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: QHHKLKALXVSMEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  13.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-trimethylsilyloxyocta-2,7-diene 在 咪唑 、 AD-mix-β 作用下， 以 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 2.0h， 生成 3-(tert-butyl-dimethyl-silanyloxy)-oct-7-en-2-one
  参考文献：
  名称：

  Sanglifehrin−Cyclophilin Interaction:  Degradation Work, Synthetic Macrocyclic Analogues, X-ray Crystal Structure, and Binding Data

  摘要：

  Sanglifehrin A (SFA) is a novel immunosuppressive natural product isolated from Streptomyces sp. A92-308110. SFA has a very strong affinity for cyclophilin A (IC50 = 6.9 +/- 0.9 nM) but is structurally different from cyclosporin A (CsA) and exerts its immunosuppressive activity via a novel mechanism. SFA has a complex molecular structure consisting of a 22-membered macrocycle, bearing in position 23 a nine-carbon tether terminated by a highly substituted spirobicyclic moiety. Selective oxidative cleavage of the C-26=C-27 exocyclic double bond affords the spirolactam containing fragment 1 and macrolide 2. The affinity of 2 for cyclophilin (IC50 = 29 +/- 2.1 nM) is essentially identical to SFA, which indicates that the interaction between SFA and cyclophilin A is mediated exclusively by the macrocyclic portion of the molecule. This observation was confirmed by the X-ray crystal structure resolved at 2.1 Angstrom of cyclophilin A complexed to macrolide 16, a close analogue of 2. The X-ray crystal structure showed that macrolide 16 binds to the same deep hydrophobic pocket of cyclophilin A as CsA. Additional valuable details of the structure-activity relationship were obtained by two different chemical approaches: (1) degradation work on macrolide 2 or (2) synthesis of a library of macrolide analogues using the ring-closing metathesis reaction as the key step. Altogether, it appears that the complex macrocyclic fragment of SFA is a highly optimized combination of multiple functionalities including an (E,E)-diene, a short polypropionate fragment, and an unusual tripeptide unit, which together provide an extremely strong affinity for cyclophilin A.

  DOI：

  10.1021/ja021327y
• 作为产物：
  描述：

  4-溴-1-丁烯 、 三甲基氯硅烷 、 丁烯酮 在 碘 、 magnesium 、 六甲基磷酰三胺 、 copper(l) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以86%的产率得到2-trimethylsilyloxyocta-2,7-diene
  参考文献：
  名称：

  新的Fe（III）介导的环丙基甲硅烷基醚的自由基级联反应。

  摘要：

  [反应：参见文本] Fe（III）介导的带有苯基取代的丁烯基侧链的环丙基醚的开环导致生成β-酮基，该基团经过5-exo环化，随后形成新的级联序列，从而形成三环醚。

  DOI：

  10.1021/ol0341703

文献信息

• PET-Oxidative Cyclization of Unsaturated Enol Silyl Ethers
  作者：Andreas Heidbreder、Jochen Mattay

  DOI：10.1016/0040-4039(92)88117-n

  日期：1992.4

  Unsaturated enol silyl ethers are irradiated in the presence of the electron transfer sensitizer 9, 10-dicyanoanthracene to form silyloxy radical cations which cyclize efficiently to yield cyclic ketones. Cyclization reactions of ε,ζ-unsaturated enol silyl ethers lead exclusively to 6-membered rings.

  在电子转移敏化剂9、10-二氰基蒽的存在下辐照不饱和的烯醇甲硅烷基醚以形成甲硅烷基氧基阳离子，其有效地环化以产生环状酮。ε，ζ-不饱和烯醇甲硅烷基醚的环化反应仅导致6元环。