(S)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-butyric acid | 214853-74-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (S)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-butyric acid
• 英文别名: (2S,4E)-2-methyl-4-[(5R)-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ylidene]butanoic acid
• CAS: 214853-74-4
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: UMNXEAZSFBALLI-RQFBLELKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(-)- α-甲基苄胺 、 (S)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-butyric acid 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以74%的产率得到(S)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-N-((S)-1-phenyl-ethyl)-butyramide
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r
• 作为产物：
  描述：

  Propionic acid (1S,5R)-5-isopropenyl-2-methyl-1-vinyl-cyclohex-2-enyl ester 在 正丁基锂 、 二异丙胺 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 为溶剂， 生成 (S)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-butyric acid 、 (R)-4-[(R)-5-Isopropenyl-2-methyl-cyclohex-2-en-(E)-ylidene]-2-methyl-butyric acid
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r

文献信息

• Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis
  作者：Sang-phyo Hong、Harriet A. Lindsay、Tripura Yaramasu、Xiaowei Zhang、Matthias C. McIntosh

  DOI：10.1021/jo010752r

  日期：2002.4.1

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.