Bis<(S)-(-)-2-methylbutyl> phosphorochloridate | 161258-05-5

• 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<(S)-(-)-2-methylbutyl> phosphorochloridate
• 英文别名: (2S)-1-[chloro-[(2S)-2-methylbutoxy]phosphoryl]oxy-2-methylbutane
• CAS: 161258-05-5
• 化学式: C₁₀H₂₂ClO₃P
• 分子量: 256.71
• InChiKey: HJDSOYRPEVZLJM-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  Bis<(S)-(-)-2-methylbutyl> phosphorochloridate 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 9.0h， 生成 6-bis[(2S)-2-methylbutoxy]phosphoryl-3-methylcyclohex-2-en-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：

  S-(-)-2-甲基-1-丁醇 在 三乙胺 、 三氯氧磷 作用下， 以 苯 为溶剂， 反应 24.0h， 以90%的产率得到Bis<(S)-(-)-2-methylbutyl> phosphorochloridate
  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

• Diastereoselective Vinyl Phosphate/β-Keto Phosphonate Rearrangements
  作者：Jianguo An、Jeffrey M. Wilson、Yi-Zhong An、David F. Wiemer

  DOI：10.1021/jo9518157

  日期：1996.1.1

  nonracemic diols and amino alcohols have been tested for their utility as chiral auxiliaries in vinyl phosphate/beta-keto phosphonate rearrangements. When (2R,4R)- or (2S,4S)-pentane-2,4-diol were employed, the diastereomeric beta-keto phosphonates obtained from three prochiral cyclohexanones gave separate resonances in their respective (31)P NMR spectra, allowing estimation of diastereomeric excess

  已经测试了几种非外消旋二醇和氨基醇在磷酸乙烯基酯/β-酮基膦酸酯重排中作为手性助剂的用途。当使用（2R，4R）-或（2S，4S）-戊烷-2,4-二醇时，由三个前手性环己酮获得的非对映体β-酮膦酸酯在其各自的（31）P NMR光谱中给出独立的共振，从而可以进行估计通过直接集成可以计算非对映体过量（de）。β-酮膦酸酯的结晶烯醇形式是从一种酮（4-（1,1-（亚乙二氧基）乙基）-4-甲基环己酮，10）获得的，其可以通过X射线衍射分析确定其绝对立体化学。当使用LTMP诱导衍生自酮10和（2R，4R）-或（2S，4S）-戊烷-2,4-二醇的磷酸乙烯基酯的重排时，得的de为2.5：1。此外，
• 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.