Bis<2(S)-Methylbutyl> 4-methyl-1-cyclohexenyl phosphate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: Bis<2(S)-Methylbutyl> 4-methyl-1-cyclohexenyl phosphate
• 英文别名: bis[(2S)-2-methylbutyl] (4-methylcyclohexen-1-yl) phosphate
• 化学式: C₁₇H₃₃O₄P
• 分子量: 332.42
• InChiKey: NEPYBSFGCAHRJT-KSCSMHSMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  Bis<2(S)-Methylbutyl> 4-methyl-1-cyclohexenyl phosphate 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以73%的产率得到2-bis[(2S)-2-methylbutoxy]phosphoryl-4-methylcyclohexan-1-one
  参考文献：
  名称：

  Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates

  摘要：

  A series of chiral auxiliaries has been tested for viability in the vinyl phosphate/beta-keto phosphonate rearrangement. While dienyl phosphates derived from ephedrine, pseudoephedrine, and isopinocampheol succumbed to competing elimination reactions, ones derived from menthol and (S)-2-methylbutanol were found to undergo rearrangement to the desired beta-keto phosphonates. The bis((S)2-methylbultyl) phosphorochloridate then was used to prepare the vinyl phosphates of the prochiral ketone 4-methylcyclohexanone, and modest diastereoselectivity was observed upon rearrangement of these phosphates to the corresponding beta-keto phosphonates. The de of this rearrangement was established by degradation of the beta-keto phosphonate to 3-methyladipic acid and determination of the optical rotation. This sequence allowed identification of the major rearrangement product as the 4R-diastereomer of beta-keto phosphonate 13. Finally, two other prochiral cyclohexanones were found to be suitable substrates for the vinyl phosphate/beta-keto phosphonate rearrangement.

  DOI：

  10.1021/jo00105a042
• 作为产物：
  描述：

  4-甲基环己酮 、 Bis<(S)-(-)-2-methylbutyl> phosphorochloridate 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到Bis<2(S)-Methylbutyl> 4-methyl-1-cyclohexenyl phosphate
  参考文献：
  名称：

  Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates

  摘要：

  A series of chiral auxiliaries has been tested for viability in the vinyl phosphate/beta-keto phosphonate rearrangement. While dienyl phosphates derived from ephedrine, pseudoephedrine, and isopinocampheol succumbed to competing elimination reactions, ones derived from menthol and (S)-2-methylbutanol were found to undergo rearrangement to the desired beta-keto phosphonates. The bis((S)2-methylbultyl) phosphorochloridate then was used to prepare the vinyl phosphates of the prochiral ketone 4-methylcyclohexanone, and modest diastereoselectivity was observed upon rearrangement of these phosphates to the corresponding beta-keto phosphonates. The de of this rearrangement was established by degradation of the beta-keto phosphonate to 3-methyladipic acid and determination of the optical rotation. This sequence allowed identification of the major rearrangement product as the 4R-diastereomer of beta-keto phosphonate 13. Finally, two other prochiral cyclohexanones were found to be suitable substrates for the vinyl phosphate/beta-keto phosphonate rearrangement.

  DOI：

  10.1021/jo00105a042

文献信息

• Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates
  作者：Yi-Zhong An、Jian Guo An、David F. Wiemer

  DOI：10.1021/jo00105a042

  日期：1994.12

  A series of chiral auxiliaries has been tested for viability in the vinyl phosphate/beta-keto phosphonate rearrangement. While dienyl phosphates derived from ephedrine, pseudoephedrine, and isopinocampheol succumbed to competing elimination reactions, ones derived from menthol and (S)-2-methylbutanol were found to undergo rearrangement to the desired beta-keto phosphonates. The bis((S)2-methylbultyl) phosphorochloridate then was used to prepare the vinyl phosphates of the prochiral ketone 4-methylcyclohexanone, and modest diastereoselectivity was observed upon rearrangement of these phosphates to the corresponding beta-keto phosphonates. The de of this rearrangement was established by degradation of the beta-keto phosphonate to 3-methyladipic acid and determination of the optical rotation. This sequence allowed identification of the major rearrangement product as the 4R-diastereomer of beta-keto phosphonate 13. Finally, two other prochiral cyclohexanones were found to be suitable substrates for the vinyl phosphate/beta-keto phosphonate rearrangement.