(E)-11-((tert-butyldimethylsilyl)oxy)undec-2-en-1-ol | 193811-90-4

• 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: (E)-11-((tert-butyldimethylsilyl)oxy)undec-2-en-1-ol
• 英文别名: 11-tert-butyldimethylsilyloxyundec-2E-en-1-ol；(E)-11-[tert-butyl(dimethyl)silyl]oxyundec-2-en-1-ol
• CAS: 193811-90-4
• 化学式: C₁₇H₃₆O₂Si
• 分子量: 300.557
• InChiKey: CYXVOMBVKCFRCT-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  20
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-11-((tert-butyldimethylsilyl)oxy)undec-2-en-1-ol 在 吡啶 、 4-甲基苯磺酸吡啶 作用下， 以 乙醇 为溶剂， 生成 (E)-ethyl (11-hydroxyundec-2-en-1-yl) carbonate
  参考文献：
  名称：

  New Synthetic Methodology toward Macrolides/Macrolactams via Palladium-Catalyzed Carbon-Heteroatom Bond-Forming Reactions

  摘要：

  利用辻-特罗斯特（Tsuji-Trost）型反应实现了 11-16 元大环内酯和 13-15 元大环内酯的简易和多功能合成。这种方法是利用碳酸乙酯与羧酸以及催化量的 Pd(PPh3)4 进行分子内环化，形成碳-叔原子共价键，无需使用化学计量试剂。

  DOI：

  10.1055/s-0030-1260812
• 作为产物：
  描述：

  11-((tert-butyldimethylsilyl)oxy)undec-2-yn-1-ol 在 红铝 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 8.0h， 以95%的产率得到(E)-11-((tert-butyldimethylsilyl)oxy)undec-2-en-1-ol
  参考文献：
  名称：

  二炔二醇天然产物强链二醇H和I的立体选择性全合成和结构修饰。

  摘要：

  已经完成了强硬二醇H和I的立体选择性全合成。合成方法包括使用CBS作为催化剂的烯-炔-酮中的酮官能团的立体选择性还原，以及Cadiot-Chodkiewicz偶联反应作为关键反应步骤。常见的醛中间体已用于合成两种强二醇。

  DOI：

  10.3762/bjoc.14.206

文献信息

• Enzyme-Substrate Complementarity Governs Access to a Cationic Reaction Manifold in the P450_BM3-Catalysed Oxidation of Cyclopropyl Fatty Acids
  作者：Max J. Cryle、Patricia Y. Hayes、James J. De Voss

  DOI：10.1002/chem.201203035

  日期：2012.12.7

  The products of cytochrome P450BM3‐catalysed oxidation of cyclopropyl‐containing dodecanoic acids are consistent with the presence of a cationic reaction intermediate, which results in efficient dehydrogenation of the rearranged probes by the enzyme. These results highlight the importance of enzyme–substrate complementarity, with a cationic intermediate occurring only when the probes used begin to

  细胞色素P450 BM3催化的含环丙​​基十二烷酸氧化的产物与阳离子反应中间体的存在是一致的，这导致了酶对重排探针的有效脱氢。这些结果突出了酶与底物互补的重要性，阳离子中间体仅在所用探针开始从该酶的理想底物上分化时才出现。这也有助于调和文献报道，该报道支持阳离子中间体与某些细胞色素P450酶/底物对的存在。
• Total Synthesis of the Annonaceous Acetogenin (+)-Asimicin. Development of a New Bidirectional Strategy
  作者：James A. Marshall、Kevin W. Hinkle

  DOI：10.1021/jo970423s

  日期：1997.8.1

  The total synthesis of the Annonaceous acetogenin (+)-asimicin is described. The approach employs the (R)-alpha-OSEM allylic stannane 7 of >95% ee and the dialdehyde 8 obtained from (S,S)-diethyl tartrate. Addition of 7 to 8 in the presence of InCl3 afforded the bis-adduct 9 in 71% yield. Tosylation and treatment with TBAF led to the core bis-tetrahydrofuran intermediate, diol 11, in 78% yield. Mono tosylation (n-BuLi, TsCl, THF-DMSO) and subsequent hydrogenolysis with LiBEt3H gave alcohol 14. The iodide 15 was coupled with the higher-order vinylcyanocuprate to afford olefin 30. This was converted to diol 31 of high ee by the Sharpless protocol. This diol yielded the epoxide 33 via the mono-trisylate 32. Addition of (R)-lithio-2-(OTBS)-3-butyne in the presence of BF3 . OEt2 afforded the alcohol 34. The SEM derivative 35 was treated with TBAF, and the resulting alcohol was converted to the butenolide 38 by a sequence involving treatment with (CF3CO)(2)O, then Pd(PPh3)(4), CO, THF-H2O, and finally AgNO3/silica gel. Cleavage of the SEM protecting group with PPTS in ethanol afforded (+)-asimicin (39).
• New Synthetic Methodology toward Macrolides/Macrolactams via Palladium-Catalyzed Carbon-Heteroatom Bond-Forming Reactions
  作者：Hidemi Yoda、Tetsuya Sengoku、Tomoya Hamamatsu、Toshiyasu Inuzuka、Masaki Takahashi

  DOI：10.1055/s-0030-1260812

  日期：2011.7

  A concise and versatile syntheses of 11-16-membered macrolides and 13-15-membered macrolactams have been achieved using a Tsuji-Trost type reaction. This approach is composed of intramolecular cyclization employing ethyl carbonate with carboxylic acids and catalytic amount of Pd(PPh3)4 to form carbon-heteroatom covalent bonds with no use of stoichiometric reagents.

  利用辻-特罗斯特（Tsuji-Trost）型反应实现了 11-16 元大环内酯和 13-15 元大环内酯的简易和多功能合成。这种方法是利用碳酸乙酯与羧酸以及催化量的 Pd(PPh3)4 进行分子内环化，形成碳-叔原子共价键，无需使用化学计量试剂。
• Stereoselective total synthesis and structural revision of the diacetylenic diol natural products strongylodiols H and I
  作者：Pamarthi Gangadhar、Sayini Ramakrishna、Ponneri Venkateswarlu、Pabbaraja Srihari

  DOI：10.3762/bjoc.14.206

  日期：——

  The stereoselective total synthesis of strongylodiol H and I has been accomplished. The synthetic procedure comprised the stereoselective reduction of a ketone functionality in an ene-yne-one employing CBS as a catalyst and a Cadiot-Chodkiewicz coupling reaction as the key reaction steps. A common aldehyde intermediate has been used for the synthesis of both strongylodiols.

  已经完成了强硬二醇H和I的立体选择性全合成。合成方法包括使用CBS作为催化剂的烯-炔-酮中的酮官能团的立体选择性还原，以及Cadiot-Chodkiewicz偶联反应作为关键反应步骤。常见的醛中间体已用于合成两种强二醇。