(5R,7S,8S,9S)-8,9-Bis-(tert-butyl-dimethyl-silanyloxy)-7-methyl-6-oxa-spiro[4.5]decan-1-one | 154373-30-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5R,7S,8S,9S)-8,9-Bis-(tert-butyl-dimethyl-silanyloxy)-7-methyl-6-oxa-spiro[4.5]decan-1-one
• 英文别名: (5R,7S,8S,9S)-8,9-bis[[tert-butyl(dimethyl)silyl]oxy]-7-methyl-6-oxaspiro[4.5]decan-4-one
• CAS: 154373-30-5
• 化学式: C₂₂H₄₄O₄Si₂
• 分子量: 428.76
• InChiKey: UOLHMXJIHGVTNI-YZVAWVHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 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,8S,9S)-8,9-Bis-(tert-butyl-dimethyl-silanyloxy)-7-methyl-6-oxa-spiro[4.5]decan-1-one 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.67h， 以98%的产率得到(6S,8S,9S,10S)-9,10-bis(tert-butyldimethylsiloxy)-8-methyl-1,7-dioxaspiro[5.5]undecan-2-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：

  3,4-二-O-乙酰-1,5-酐-2,6-双脱氧-L-阿拉伯-己-1-糖醇 在 咪唑 、 甲醇 、 camphor-10-sulfonic acid 、 叔丁基锂 、 sodium 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 反应 33.0h， 生成 (5R,7S,8S,9S)-8,9-Bis-(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

文献信息

• A convenient route to spirocyclic C-glycosides. Demonstration that ring strain release can override normal operation of the ferrier rearrangement
  作者：Leo A. Paquette、Uta Dullweber、Lora D. Cowgill

  DOI：10.1016/s0040-4039(00)61439-9

  日期：1993.12

  The response of glycals substituted at C(1) with a tertiary cyclic carbinol is shown to vary strikingly as a function of ring size.
• Practical Synthesis of Spirocyclic Bis-C,C-glycosides. Mechanistic Models in Explanation of Rearrangement Stereoselectivity and the Bifurcation of Reaction Pathways
  作者：Leo A. Paquette、Margaret J. Kinney、Uta Dullweber

  DOI：10.1021/jo962020i

  日期：1997.3.1

  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.