1-[(5R,6S)-5-(tert-Butyl-dimethyl-silanyloxy)-6-methyl-5,6-dihydro-4H-pyran-2-yl]-cyclobutanol | 188681-23-4

• 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: 1-[(5R,6S)-5-(tert-Butyl-dimethyl-silanyloxy)-6-methyl-5,6-dihydro-4H-pyran-2-yl]-cyclobutanol
• 英文别名: 1-((2S,3R)-3-{[Tert-butyl(dimethyl)silyl]oxy}-2-methyl-3,4-dihydro-2H-pyran-6-YL)cyclobutanol；1-[(2S,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-3,4-dihydro-2H-pyran-6-yl]cyclobutan-1-ol
• CAS: 188681-23-4
• 化学式: C₁₆H₃₀O₃Si
• 分子量: 298.498
• InChiKey: KYVLAJFSGKCPRK-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.98
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-[(5R,6S)-5-(tert-Butyl-dimethyl-silanyloxy)-6-methyl-5,6-dihydro-4H-pyran-2-yl]-cyclobutanol 在 camphor-10-sulfonic acid 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以17%的产率得到(5R,7S,8R)-8-(tert-Butyl-dimethyl-silanyloxy)-7-methyl-6-oxa-spiro[4.5]decan-1-one
  参考文献：
  名称：

  Practical Synthesis of Spirocyclic Bis-C,C-glycosides. Mechanistic Models in Explanation of Rearrangement Stereoselectivity and the Bifurcation of Reaction Pathways

  摘要：

  The susceptibility of glycal-derived carbinols to acid-catalyzed ring expansion is described. In the systems prepared from cyclopentanone, Ferrier ionization precedes the pinacol-like Wagner-Meerwein shift, thermodynamic control operates, and high stereoselectivity is seen if a C(6) substituent is present. In contrast, the adducts to cyclobutanone exhibit release of ring strain under kinetically controlled conditions and intercept the oxonium species reversibly formed via direct proton transfer. The results show that the substituents positioned on the glycal ring have a pronounced influence on whether a chair-like or twist-boat transition state geometry is adopted primarily. The composite reaction profiles reveal for the first time the fundamental importance of exothermicity and of substitution in these spiro glycosidation reactions. Since optical activity is preserved in all instances, the utility of this chemistry for the synthesis of bis-C,C-glycosides and more complex oxacyclics appears promising.

  DOI：

  10.1021/jo962020i
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 叔丁基锂 作用下， 生成 1-[(5R,6S)-5-(tert-Butyl-dimethyl-silanyloxy)-6-methyl-5,6-dihydro-4H-pyran-2-yl]-cyclobutanol
  参考文献：
  名称：

  Practical Synthesis of Spirocyclic Bis-C,C-glycosides. Mechanistic Models in Explanation of Rearrangement Stereoselectivity and the Bifurcation of Reaction Pathways

  摘要：

  The susceptibility of glycal-derived carbinols to acid-catalyzed ring expansion is described. In the systems prepared from cyclopentanone, Ferrier ionization precedes the pinacol-like Wagner-Meerwein shift, thermodynamic control operates, and high stereoselectivity is seen if a C(6) substituent is present. In contrast, the adducts to cyclobutanone exhibit release of ring strain under kinetically controlled conditions and intercept the oxonium species reversibly formed via direct proton transfer. The results show that the substituents positioned on the glycal ring have a pronounced influence on whether a chair-like or twist-boat transition state geometry is adopted primarily. The composite reaction profiles reveal for the first time the fundamental importance of exothermicity and of substitution in these spiro glycosidation reactions. Since optical activity is preserved in all instances, the utility of this chemistry for the synthesis of bis-C,C-glycosides and more complex oxacyclics appears promising.

  DOI：

  10.1021/jo962020i