(5R,7S,8R,9S)-8-[tert-butyl(dimethyl)silyl]oxy-2,2,7-trimethyl-1,3-dioxaspiro[4.4]nonane-9-carbaldehyde | 1160556-72-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5R,7S,8R,9S)-8-[tert-butyl(dimethyl)silyl]oxy-2,2,7-trimethyl-1,3-dioxaspiro[4.4]nonane-9-carbaldehyde
• CAS: 1160556-72-8
• 化学式: C₁₇H₃₂O₄Si
• 分子量: 328.524
• InChiKey: NZFSEVFQAUJNBB-ZJOBFFGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5R,7S,8R,9S)-8-[tert-butyl(dimethyl)silyl]oxy-2,2,7-trimethyl-1,3-dioxaspiro[4.4]nonane-9-carbaldehyde 在 吡啶 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 甲醇 、 Schwartz's reagent 、 lanthanum(III) nitrate hexahydrate 、 氢氟酸 、 甲基锂 、 碘 、 potassium carbonate 、 9-硼双环[3.3.1]壬烷 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 偶氮二甲酸二乙酯 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 二甲基亚砜 、 甲苯 、 乙腈 为溶剂， 反应 2.0h， 生成 characiol
  参考文献：
  名称：

  Total Synthesis of Natural and Non-Natural Δ^5,6Δ^12,13-Jatrophane Diterpenes and Their Evaluation as MDR Modulators

  摘要：

  We report the details of the total synthesis of natural and non-natural jatropha-5,12-dienes. The successful tactic for the assembly of the strained trans-bicyclo[10.3.0]pentadecane scaffold employed a B-alkyl Suzuki-Miyaura cross-coupling for the formation of the C5/C6 double bond and a ring-closing metathesis for the construction of the C12/C13 double bond. The key step of the synthesis of the cyclopentane fragment, an uncatalyzed intramolecular carbonyl-ene reaction, was studied computationally by DFT calculations. The members of the ensemble of synthetic natural and non-natural jatrophanes were subsequently examined as modulators for the ABCB1, ABCG2, and ABCC1 efflux proteins, which are associated with multidrug resistance in cancer chemotherapy.

  DOI：

  10.1021/jo1019738
• 作为产物：
  描述：

  在 lithium aluminium tetrahydride 、 4-甲基苯磺酸吡啶 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 癸烷 为溶剂， 反应 1.25h， 生成 (5R,7S,8R,9S)-8-[tert-butyl(dimethyl)silyl]oxy-2,2,7-trimethyl-1,3-dioxaspiro[4.4]nonane-9-carbaldehyde
  参考文献：
  名称：

  Total Synthesis of Natural and Non-Natural Δ^5,6Δ^12,13-Jatrophane Diterpenes and Their Evaluation as MDR Modulators

  摘要：

  We report the details of the total synthesis of natural and non-natural jatropha-5,12-dienes. The successful tactic for the assembly of the strained trans-bicyclo[10.3.0]pentadecane scaffold employed a B-alkyl Suzuki-Miyaura cross-coupling for the formation of the C5/C6 double bond and a ring-closing metathesis for the construction of the C12/C13 double bond. The key step of the synthesis of the cyclopentane fragment, an uncatalyzed intramolecular carbonyl-ene reaction, was studied computationally by DFT calculations. The members of the ensemble of synthetic natural and non-natural jatrophanes were subsequently examined as modulators for the ABCB1, ABCG2, and ABCC1 efflux proteins, which are associated with multidrug resistance in cancer chemotherapy.

  DOI：

  10.1021/jo1019738

文献信息

• Total Synthesis of Jatrophane Diterpenes from <i>Euphorbia characias</i>
  作者：Christoph Schnabel、Martin Hiersemann

  DOI：10.1021/ol900819u

  日期：2009.6.18

  The enantioselective total synthesis of the jatrophane diterpene (-)-15-O-acetyl-3-O-propionylcharaciol is described. Starting from an advanced cyclopentane building block, a B-alkyl Suzuki-Miyaura cross-coupling and carbonyl addition were utilized to assemble a fully functionalized triene, and a ring-closing metathesis was then employed to construct the rigid 12-membered ring. Twenty-five years after the original report on the isolation of the natural product, our total synthesis unambiguously corroborates the original tentative structural assignment.
• Total Synthesis of Natural and Non-Natural Δ^5,6Δ^12,13-Jatrophane Diterpenes and Their Evaluation as MDR Modulators
  作者：Christoph Schnabel、Katja Sterz、Henrik Müller、Julia Rehbein、Michael Wiese、Martin Hiersemann

  DOI：10.1021/jo1019738

  日期：2011.1.21

  We report the details of the total synthesis of natural and non-natural jatropha-5,12-dienes. The successful tactic for the assembly of the strained trans-bicyclo[10.3.0]pentadecane scaffold employed a B-alkyl Suzuki-Miyaura cross-coupling for the formation of the C5/C6 double bond and a ring-closing metathesis for the construction of the C12/C13 double bond. The key step of the synthesis of the cyclopentane fragment, an uncatalyzed intramolecular carbonyl-ene reaction, was studied computationally by DFT calculations. The members of the ensemble of synthetic natural and non-natural jatrophanes were subsequently examined as modulators for the ABCB1, ABCG2, and ABCC1 efflux proteins, which are associated with multidrug resistance in cancer chemotherapy.