(R)-6-<<(tert-butyldiphenylsilyl)oxy>methyl>-3,4,5,6-tetrahydro-2H-pyran-2-one | 175398-33-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (R)-6-<<(tert-butyldiphenylsilyl)oxy>methyl>-3,4,5,6-tetrahydro-2H-pyran-2-one
• 英文别名: (R)-6-(tert-butyldiphenylsilyloxymethyl)tetrahydro-2H-pyran-2-one；(5R)-6-tert-butyldiphenylsilyloxy-5-hydroxyhexanoic acid δ-lactone；6-((tert-butyldiphenylsilyloxy)methyl)-tetrahydropyran-2-one；(6R)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]oxan-2-one
• CAS: 175398-33-1
• 化学式: C₂₂H₂₈O₃Si
• 分子量: 368.548
• InChiKey: QMTLYJBAALMILW-GOSISDBHSA-N

物化性质

• 沸点：
  462.1±27.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-6-<<(tert-butyldiphenylsilyl)oxy>methyl>-3,4,5,6-tetrahydro-2H-pyran-2-one 在 正丁基锂 、 六甲基二硅氮烷 、 苯基溴化硒 、 双氧水 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 1.92h， 以79%的产率得到(R)-6-(((tert-butyldiphenylsilyl)oxy)methyl)-5,6-dihydro-2H-pyran-2-one
  参考文献：
  名称：

  (R)-Argentilactone 和 (R)-Goniothalamin 使用自由基光氧化还原方法合成 α,β-不饱和 δ-内酯

  摘要：

  α,β-不饱和 δ-内酯是在多种药理活性天然产物中发现的结构基序。事实上，不饱和内酯通常负责生物活性。在此，我们报告了一种基于光氧化还原过程介导的光氧化还原分子间碘内酯化合成 (R)-argentilactone 和 (R)-goniothalamin 的新方法。这种新方法已经在我们的研究小组中使用，是一种新方法，可以实现多种含有 α,β-不饱和 δ-内酯的天然产物。

  DOI：

  10.1055/a-1550-7659
• 作为产物：
  描述：

  5-己烯酸 在 咪唑 、 (DHQD)2AQN 、 K₂OsO₂(OH)2 、 碳酸氢钠 、 potassium carbonate 、 苯甲醚 、 三氟乙酸 、 potassium hexacyanoferrate(III) 作用下， 以 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 137.5h， 生成 (R)-6-<<(tert-butyldiphenylsilyl)oxy>methyl>-3,4,5,6-tetrahydro-2H-pyran-2-one
  参考文献：
  名称：

  Determination of the Relative and Absolute Stereochemistry of Fostriecin (CI-920)

  摘要：

  The absolute stereochemistry of fostriecin (1, CI-920), a potent antitumor antibiotic presently in Phase I clinical trials at NCI, was determined to be 5R,8R,9R,11R. 2D H-1-H-1 NMR. NOE experiments conducted on the cyclic phosphate derivative 2 and acetonide revealed a syn-diol stereochemical relationship between C8 and C9 and an anti-diol stereochemical relationship between C9 and C11, respectively. The 5R absolute configuration assignment was confirmed by synthesis of the degradation product 8 previously disclosed. Additional degradation studies of 1 to provide 7 and chiral-phase HPLC comparison with a sample of known chirality established the absolute stereochemistry of C11 to be R. This, along with the relative stereochemical assignments established the full set of absolute stereochemistry assignments for 1.

  DOI：

  10.1021/jo962166h

文献信息

• Total Synthesis of (−)-Histrionicotoxin 285A and (−)-Perhydrohistrionicotoxin
  作者：James M. Macdonald、Helen T. Horsley、John H. Ryan、Simon Saubern、Andrew B. Holmes

  DOI：10.1021/ol801604z

  日期：2008.10.2

  Starting from commercially available ( S)-glycidol, and via a common intermediate, the total synthesis of (-)-histrionicotoxin 285A and (-)-perhydrohistrionicotoxin has been achieved. Key to this synthesis was the efficient construction of a six-membered, chiral, cyclic nitrone.

  从可商购获得的（S）-缩水甘油开始，并通过共同的中间体，已经完成了（-）-组织变质毒素285A和（-）-过氢组织变质毒素的全合成。合成的关键是有效地构建六元手性环状硝酮。
• A new catalytic oxidative cleavage reaction to furnish lactones
  作者：Stefanie Roth、Christian B. W. Stark

  DOI：10.1039/b815135k

  日期：——

  A highly efficient oxidative cleavage reaction of THF and THP alcohols to gamma- and delta-lactones using catalytic PCC (1 mol%) and periodic acid as terminal oxidant is presented.

  提出了使用催化PCC（1 mol％）和高碘酸作为末端氧化剂的THF和THP醇高效氧化裂解反应，生成γ-和δ-内酯的方法。
• A chemoenzymatic preparation of both enantiomers of ω-hydroxymethyl-substituted lactones
  作者：Didier Buisson、Robert Azerad

  DOI：10.1016/0957-4166(95)00408-4

  日期：1996.1

  (R)- and (S)-delta-hydroxymethyl vaterolactone and epsilon-hydroxymethyl caprolactone were prepared as tert-butyldiphenylsilyl derivatives, in good yields and high enantiomeric purities, in a 5 step sequence, starting from the microbial stereospecific reduction of ethyl 2-oxocyclopentane or 2-oxocyclohexane carboxylates respectively.
• Total Synthesis of (R)-Argentilactone and (R)-Goniothalamin Using a Free-Radical Photoredox Approach to α,β-Unsaturated δ-Lactones
  作者：Alejandro Cordero-Vargas、Francisco J. Fuentes-Pantoja

  DOI：10.1055/a-1550-7659

  日期：2021.12

  α,β-Unsaturated δ-lactones are structural motifs found in diverse pharmacologically active natural products. In fact, the unsaturated lactone is often responsible for the biological activity. Herein, we report a new approach for the syntheses of (R)-argentilactone and (R)-goniothalamin based on a photoredox intermolecular iodolactonization mediated by a photoredox process. This new approach, already

  α,β-不饱和 δ-内酯是在多种药理活性天然产物中发现的结构基序。事实上，不饱和内酯通常负责生物活性。在此，我们报告了一种基于光氧化还原过程介导的光氧化还原分子间碘内酯化合成 (R)-argentilactone 和 (R)-goniothalamin 的新方法。这种新方法已经在我们的研究小组中使用，是一种新方法，可以实现多种含有 α,β-不饱和 δ-内酯的天然产物。
• Determination of the Relative and Absolute Stereochemistry of Fostriecin (CI-920)
  作者：Dale L. Boger、Masataka Hikota、Bryan M. Lewis

  DOI：10.1021/jo962166h

  日期：1997.3.1

  The absolute stereochemistry of fostriecin (1, CI-920), a potent antitumor antibiotic presently in Phase I clinical trials at NCI, was determined to be 5R,8R,9R,11R. 2D H-1-H-1 NMR. NOE experiments conducted on the cyclic phosphate derivative 2 and acetonide revealed a syn-diol stereochemical relationship between C8 and C9 and an anti-diol stereochemical relationship between C9 and C11, respectively. The 5R absolute configuration assignment was confirmed by synthesis of the degradation product 8 previously disclosed. Additional degradation studies of 1 to provide 7 and chiral-phase HPLC comparison with a sample of known chirality established the absolute stereochemistry of C11 to be R. This, along with the relative stereochemical assignments established the full set of absolute stereochemistry assignments for 1.