(E)-3-methoxyallyl propanoate | 65500-01-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-3-methoxyallyl propanoate
• 英文别名: (E)-3-methoxy-2-propen-1-yl propanoate；(2E)-3-methoxy-2-propenyl propionate；[(E)-3-methoxyprop-2-enyl] propanoate
• CAS: 65500-01-8
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: AABXMRVVZBKSPQ-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  (E)-3-methoxyallyl propanoate 在 三乙胺 、 lithium diisopropyl amide 作用下， 反应 1.05h， 生成 (2SR,3RS)-3-methoxy-2-methyl-4-petenoic acid
  参考文献：
  名称：

  Stereochemical control in the ester enolate Claisen rearrangement. 2. Chairlike vs boatlike transition-state selection

  摘要：

  The preference for chair- and boatlike transition-state geometries in the ester enolate Claisen rearrangement of straight chain, carbocyclic, and heterocyclic propanoates was investigated. A novel stereoelectronic effect in pyranoid and furanoid glycal systems leads to a significant relative stabilization of the boatlike vs the chairlike TS double-ended-dagger. The preferred transition state in six- and five-membered carbocyclic systems is highly dependent on steric factors, as the energy difference between chair- and boatlike TS double-ended-dagger tends to be small. With straight-chain substrates, a significant contribution of the boatlike TS double-ended-dagger to the rearrangement product mixture is only expected in bis-donor substituted allylic esters.

  DOI：

  10.1021/jo00011a023
• 作为产物：
  描述：

  3-methoxy-2-propen-1-ol 、 丙酸酐 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 以87%的产率得到(E)-3-methoxyallyl propanoate
  参考文献：
  名称：

  Stereochemical control in the ester enolate Claisen rearrangement. 2. Chairlike vs boatlike transition-state selection

  摘要：

  The preference for chair- and boatlike transition-state geometries in the ester enolate Claisen rearrangement of straight chain, carbocyclic, and heterocyclic propanoates was investigated. A novel stereoelectronic effect in pyranoid and furanoid glycal systems leads to a significant relative stabilization of the boatlike vs the chairlike TS double-ended-dagger. The preferred transition state in six- and five-membered carbocyclic systems is highly dependent on steric factors, as the energy difference between chair- and boatlike TS double-ended-dagger tends to be small. With straight-chain substrates, a significant contribution of the boatlike TS double-ended-dagger to the rearrangement product mixture is only expected in bis-donor substituted allylic esters.

  DOI：

  10.1021/jo00011a023

文献信息

• Enolate Claisen rearrangement of esters from furanoid and pyranoid glycals
  作者：Robert E. Ireland、Suvit Thaisrivongs、Noel Vanier、C. S. Wilcox

  DOI：10.1021/jo01289a012

  日期：1980.1
• IRELAND, ROBERT E.;WIPF, PETER;XIANG, JIA-NING, J. ORG. CHEM. , 56,(1991) N1, C. 3572-3582
  作者：IRELAND, ROBERT E.、WIPF, PETER、XIANG, JIA-NING

  DOI：——

  日期：——
• Stereochemical control in the ester enolate Claisen rearrangement. 2. Chairlike vs boatlike transition-state selection
  作者：Robert E. Ireland、Peter Wipf、Jia Ning Xiang

  DOI：10.1021/jo00011a023

  日期：1991.5

  The preference for chair- and boatlike transition-state geometries in the ester enolate Claisen rearrangement of straight chain, carbocyclic, and heterocyclic propanoates was investigated. A novel stereoelectronic effect in pyranoid and furanoid glycal systems leads to a significant relative stabilization of the boatlike vs the chairlike TS double-ended-dagger. The preferred transition state in six- and five-membered carbocyclic systems is highly dependent on steric factors, as the energy difference between chair- and boatlike TS double-ended-dagger tends to be small. With straight-chain substrates, a significant contribution of the boatlike TS double-ended-dagger to the rearrangement product mixture is only expected in bis-donor substituted allylic esters.