(E)-6-((tert-butyldiphenylsilyl)oxy)-3-methylhex-2-enal | 1276069-79-4

• 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)-6-((tert-butyldiphenylsilyl)oxy)-3-methylhex-2-enal
• CAS: 1276069-79-4
• 化学式: C₂₃H₃₀O₂Si
• 分子量: 366.576
• InChiKey: PQYDZOJCSGYKAA-LVZFUZTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  26.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-6-((tert-butyldiphenylsilyl)oxy)-3-methylhex-2-enal 在 盐酸 、 lithium aluminium tetrahydride 、 正丁基锂 、 4-甲基苯磺酸吡啶 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.58h， 生成 tert-butyl(((E)-5-((4R,5S)-2,2-dimethyl-6-methylene-5-((phenylthio)methyl)-1,3-dioxepan-4-yl)-4-methylpent-4-en-1-yl)oxy)diphenylsilane
  参考文献：
  名称：

  Syntheses and Biological Evaluation of Costunolide, Parthenolide, and Their Fluorinated Analogues

  摘要：

  Inspired by the biosynthesis of sesquiterpene lactones (SLs), herein we report the asymmetric total synthesis of the germacrane ring (24). The synthetic strategy features a selective aldol reaction between beta,gamma-unsaturated chiral sulfonylamide 15a and aldehyde 13, as well as the intramolecular alpha-alkylation of sulfone 21 to construct a 10-membered carbocylic ring. The key intermediate 24 can be used to prepare the natural products costunolide and parthenolide (PTL), which are the key precursors for transformation into other SLs. Furthermore, the described synthetic sequences are amenable to the total synthesis of SL analogues, such as trifluoro-methylated analogues 32 and 45. Analogues 32 and 45 maintained high activities against a series of cancer cell lines compared to their parent PTL and costunolide, respectively. In addition, 32 showed enhanced tolerance to acidic media compared with PTL. To our surprise, PTL and 32 showed comparable half-lives in rat plasma and in the presence of human liver microsomes.

  DOI：

  10.1021/acs.jmedchem.5b00915
• 作为产物：
  描述：

  (E)-6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-en-1-ol 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以92%的产率得到(E)-6-((tert-butyldiphenylsilyl)oxy)-3-methylhex-2-enal
  参考文献：
  名称：

  Syntheses and Biological Evaluation of Costunolide, Parthenolide, and Their Fluorinated Analogues

  摘要：

  Inspired by the biosynthesis of sesquiterpene lactones (SLs), herein we report the asymmetric total synthesis of the germacrane ring (24). The synthetic strategy features a selective aldol reaction between beta,gamma-unsaturated chiral sulfonylamide 15a and aldehyde 13, as well as the intramolecular alpha-alkylation of sulfone 21 to construct a 10-membered carbocylic ring. The key intermediate 24 can be used to prepare the natural products costunolide and parthenolide (PTL), which are the key precursors for transformation into other SLs. Furthermore, the described synthetic sequences are amenable to the total synthesis of SL analogues, such as trifluoro-methylated analogues 32 and 45. Analogues 32 and 45 maintained high activities against a series of cancer cell lines compared to their parent PTL and costunolide, respectively. In addition, 32 showed enhanced tolerance to acidic media compared with PTL. To our surprise, PTL and 32 showed comparable half-lives in rat plasma and in the presence of human liver microsomes.

  DOI：

  10.1021/acs.jmedchem.5b00915

文献信息

• Efficient One-to-One Coupling of Easily Available 1,3-Dienes with Carbon Dioxide
  作者：Jun Takaya、Kota Sasano、Nobuharu Iwasawa

  DOI：10.1021/ol2002094

  日期：2011.4.1

  reaction of atmospheric pressure carbon dioxide with 1,3-dienes is realized for the first time through PSiP-pincer type palladium-catalyzed hydrocarboxylation. The reaction is applicable to various 1,3-dienes including easily available chemical feedstock such as 1,3-butadiene and isoprene. This protocol affords a highly useful method for the synthesis of β,γ-unsaturated carboxylic acid derivatives from

  通过PSiP-钳子型钯催化的加氢羧化反应，首次实现了大气压二氧化碳与1,3-二烯的高效一对一偶联反应。该反应适用于各种1，3-二烯，包括容易获得的化学原料，例如1，3-丁二烯和异戊二烯。该方案为从CO 2合成β，γ-不饱和羧酸衍生物提供了一种非常有用的方法。