di-2-(1R,2S,5R)menthyl (2-fluorophenyl)hydroxymethylphosphonate | 889103-64-4

• 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: di-2-(1R,2S,5R)menthyl (2-fluorophenyl)hydroxymethylphosphonate
• 英文别名: di-[(1R,2S,5R)-(-)-menth-2-yl] hydroxy-(2-fluorophenyl)methylphosphonate；di(1R,2S,5R)-menthyl hydroxy(2-fluorophenyl)methylphosphonate
• CAS: 889103-64-4
• 化学式: C₂₇H₄₄FO₄P
• 分子量: 482.616
• InChiKey: BTMZUQIPLOYBMO-AQIOLCJHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.96
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  di-2-(1R,2S,5R)menthyl (2-fluorophenyl)hydroxymethylphosphonate 在 重铬酸吡啶 、 三甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到di-(1R,2S,5R)-menthyl 2-fluorobenzoylphosphonate
  参考文献：
  名称：

  不对称还原α-和β-酮膦酸酯的有效方法

  摘要：

  开发了一种高效且通用的方法，该方法使用衍生自硼氢化钠和1-（+）-或d-（-）-酒石酸的手性反应物不对称还原α-和β-酮膦酸酯。该方法被用于许多生物有趣对映体纯产品的制备：含2,3- epoxypropylphosphonate 11，2-羟基-3-氨基丙基膦酸14（磷酸- GABOB），磷酸-肉碱19，和其他在多克规模。

  DOI：

  10.1016/j.tet.2007.04.101
• 作为产物：
  描述：

  di-(1R,2S,5R)-menthyl 2-fluorobenzoylphosphonate 在 (S,S)-Na[BH₂(tartrate)] 作用下， 以 四氢呋喃 为溶剂， 生成 di-2-(1R,2S,5R)menthyl (2-fluorophenyl)hydroxymethylphosphonate
  参考文献：
  名称：

  Enantioselective reduction of ketophosphonates using chiral acid adducts with sodium borohydride

  摘要：

  A method for asymmetric reduction of alpha- and beta-ketophosphonates using a chiral complex prepared from sodium borohydride and D- or L-tartaric acid is developed. Reduction of alpha- or beta-ketophosphonates by these reagents led to formation of corresponding (S)- or (R)-hydroxyphosphonates. Reduction of chiral di(1R,2S,5R)-menthylketophosphonates by the chiral complex NaBH4/(R,R)-tartaric acid due to the dual compliant asymmetric induction resulted in increased stereoselectivity of the reaction and led to formation of the hydroxyphosphonates with ee 90% or higher. On the other hand, reduction of di(1R,2S,5R)-methylketophosphonates by the chiral complex NaBH4/(S,S)-tartaric acid proceeded as non-compliant dual asymmetric induction and resulted in decreased reaction stereoselectivity leading to formation of hydroxyphosphonates with similar to 45-60% ee. The developed methodology was applied to the synthesis of (R)-phosphocarnifine in multigram amounts.

  DOI：

  10.1134/s1070363206070048

文献信息

• Synthesis of optically active hydroxyphosphonates
  作者：Irina Guliaiko、Vitaly Nesterov、Sergei Sheiko、Oleg I. Kolodiazhnyi、Matthias Freytag、Peter G. Jones、Reinhard Schmutzler

  DOI：10.1002/hc.20391

  日期：2008.3

  ketophosphonates was carried out by the chiral complex of NaBH4-L-proline, owing to the double asymmetric induction at the α-carbon atom. The hydroxyphosphonates obtained were isolated in a diastereomerically pure state and were transformed to the optically active, free hydroxyalkylphosphonic acids. The (R)-configuration of one of them was proved by X-ray crystal structure analysis. © 2008 Wiley Periodicals

  用硼氢化钠还原二薄荷基酮膦酸酯涉及在 α-碳原子上的不对称诱导，导致形成的 α-羟基膦酸酯的 (R)-对映体略过量。如果通过 NaBH4-L-脯氨酸的手性络合物进行手性二薄荷基酮膦酸酯的还原，由于在 α-碳原子上的双不对称诱导，可以获得更高的 ee 纯度。获得的羟基膦酸酯以非对映异构纯状态分离，并转化为旋光的游离羟基烷基膦酸。通过 X 射线晶体结构分析证明了其中之一的 (R)-构型。© 2008 Wiley Periodicals, Inc. 杂原子化学 19:133–139, 2008; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20391
• Enantioselective Synthesis of α-Hydroxyalkylphosphonates
  作者：V. V. Nesterov、O. I. Kolodyazhnyi

  DOI：10.1007/s11176-005-0386-8

  日期：2005.7