[(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-hex-3-enoate | 187950-73-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: [(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-hex-3-enoate
• CAS: 187950-73-8
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: RNMDDTVZFPYTIE-PORFMDCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-hex-3-enoate 在 dirhodium tetraacetate 、 ABSA 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.83h， 生成
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j
• 作为产物：
  描述：

  反式-3-己烯酸 、 D-(-)-泛酰内酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以80%的产率得到[(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-hex-3-enoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j

文献信息

• A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds
  作者：Priyadarshanie Bulugahapitiya、Yannick Landais、Liliana Parra-Rapado、Denis Planchenault、Valéry Weber

  DOI：10.1021/jo961952j

  日期：1997.3.1

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.