di-[(1R,2S,5R)-(-)-menth-2-yl] piperonoylphosphonate | 943975-08-4

• 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-[(1R,2S,5R)-(-)-menth-2-yl] piperonoylphosphonate
• 英文别名: di(1R,2S,5R)-menthyl piperonoylphosphonate；1,3-benzodioxol-5-yl-bis[[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxy]phosphorylmethanone
• CAS: 943975-08-4
• 化学式: C₂₈H₄₃O₆P
• 分子量: 506.62
• InChiKey: PUXYNJIUWTXGCB-WONFGVIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  di-[(1R,2S,5R)-(-)-menth-2-yl] piperonoylphosphonate 在 (S,S)-Na[BH₂(tartrate)] 作用下， 以 四氢呋喃 为溶剂， 生成 di-[(1R,2S,5R)-(-)-menth-2-yl] hydroxy-(piperonyl)phosphonate
  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
• 作为产物：
  描述：

  hydrogen di[(1R,2S,5R)-menthyl] phosphite 在 重铬酸吡啶 、 三甲基氯硅烷 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 di-[(1R,2S,5R)-(-)-menth-2-yl] piperonoylphosphonate
  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

文献信息

• Enantioselective reduction of ketophosphonates using adducts of chiral natural acids with sodium borohydride
  作者：E.V. Gryshkun、V. Nesterov、O. I. Kolodyazhnyi

  DOI：10.3998/ark.5550190.0013.409

  日期：——

  asymmetric reduction of αand β ketophosphonates using chiral complexes prepared from sodium borohydride and natural aminoacids or tartaric acids was developed. Reduction of α or β ketophosphonates by these reagents led to formation of chiral (S)or (R)hydroxyphosphonates. Reduction of chiral di-(1R,2S,5R)-menthylketophosphonates by the chiral complexes NaBH4/(R,R)-proline or NaBH4/(R,R)-tartaric acid due to

  开发了一种使用由硼氢化钠和天然氨基酸或酒石酸制备的手性配合物不对称还原 α 和 β 酮膦酸酯的方法。这些试剂还原 α 或 β 酮膦酸酯导致手性 (S) 或 (R) 羟基膦酸酯的形成。由于双匹配不对称诱导，手性复合物 NaBH4/(R,R)-脯氨酸或 NaBH4/(R,R)-酒石酸还原手性二-(1R,2S,5R)-薄荷基酮膦酸酯导致立体选择性增加反应并导致羟基膦酸酯的形成高达 90% ee 或更高。使用 2-羟基-3 氯丙基膦酸二甲酯作为制备多克数量的多种生物活性化合物的 chiron。
• New Method for the Asymmetric Reduction of Ketophosphonates
  作者：Vitaly V. Nesterov、Oleg I. Kolodiazhnyi

  DOI：10.1080/10426500701807251

  日期：2008.1.14

  Chiral reducing reactants were prepared from lithium, sodium, or tetrabutylammonium borohydrides and (S)- or (R)-tartaric acids.
• Enantioselective reduction of ketophosphonates using chiral acid adducts with sodium borohydride
  作者：V. V. Nesterov、O. I. Kolodyazhnyi

  DOI：10.1134/s1070363206070048

  日期：2006.7

  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.
• Efficient method for the asymmetric reduction of α- and β-ketophosphonates
  作者：V.V. Nesterov、O.I. Kolodiazhnyi

  DOI：10.1016/j.tet.2007.04.101

  日期：2007.7

  versatile method for the asymmetric reduction of α- and β-ketophosphonates using chiral reactant derived from sodium borohydride and l-(+)- or d-(−)-tartaric acid is developed. The methodology was used for the preparation of a number of biologically interesting enantiomerically pure products: including 2,3-epoxypropylphosphonate 11, 2-hydroxy-3-aminopropylphosphonic acid 14 (phospho-GABOB), phospho-carnitine

  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。