di(1R,2S,5R)-menthyl (S)-hydroxy(phenyl)methylphosphonate | 889103-61-1

• 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)-menthyl (S)-hydroxy(phenyl)methylphosphonate
• 英文别名: Bis((1r,2s,5r)-2-isopropyl-5-methylcyclohexyl) ((s)-hydroxy(phenyl)methyl)phosphonate；(S)-bis[[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxy]phosphoryl-phenylmethanol
• CAS: 889103-61-1
• 化学式: C₂₇H₄₅O₄P
• mdl: MFCD09863812
• 分子量: 464.626
• InChiKey: DQRWNVQUCUAZIB-QUAWNFPGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.777
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  di(1R,2S,5R)-menthyl (S)-hydroxy(phenyl)methylphosphonate 在 盐酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 72.0h， 以50%的产率得到(-)-(S)-1-phenyl-1-hydroxymethylphosphonic acid
  参考文献：
  名称：

  使用手性天然酸与硼氢化钠的加合物对映选择性还原酮膦酸盐

  摘要：

  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。

  DOI：

  10.3998/ark.5550190.0013.409
• 作为产物：
  描述：

  di-(1R,2S,5R)-menthyl α-hydroxybenzylphosphonate 在 sodium tetrahydroborate 、 重铬酸吡啶 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 di(1R,2S,5R)-menthyl (S)-hydroxy(phenyl)methylphosphonate
  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

• Asymmetric synthesis of α-substituted alkylphosphonates based on symmetrical dialkyl phosphites
  作者：O. I. Kolodiazhnyi、E. V. Grishkun、S. Sheiko、O. Demchuk、H. Thoennessen、P. Jones、R. Schmutzler

  DOI：10.1007/bf02496414

  日期：1999.8

  Chiral C2-symmetrical dialkyl phosphites and C3-symmetrical trialkyl phosphites, derived from (−)-borneol, (−)-menthol, and 1,2∶5,6-di-O-isopropylidene-α-d-glucofuranose, were studied as the starting reagents for the preparation of chiral organophosphorus compounds. The reactions of C2-symmetrical dialkyl phosphites and C3-symmetrical trialkyl phosphites with aldehydes and amines or aldehydes are accompanied

  研究了衍生自 (-)-冰片、(-)-薄荷醇和 1,2∶5,6-二-O-异亚丙基-α-d-呋喃葡萄糖的手性 C2-对称二烷基亚磷酸酯和 C3-对称三烷基亚磷酸酯作为制备手性有机磷化合物的起始试剂。C2-对称亚磷酸二烷基酯和 C3-对称亚磷酸三烷基酯与醛和胺或醛的反应伴随着在 α-碳原子上的不对称诱导，分别产生光学活性的 α-氨基烷基膦酸酯或 α-羟基烷基膦酸酯。反应的立体选择性取决于起始化合物的结构和反应条件。
• 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
• Chiral symmetric phosphoric acid esters as sources of optically active organophosphorus compounds
  作者：Oleg I Kolodiazhnyi、Evgen V Grishkun、Serge Sheiko、Oleg Demchuk、Holger Thoennessen、Peter G Jones、Reinhard Schmutzler

  DOI：10.1016/s0957-4166(98)00166-9

  日期：1998.5

  Chiral symmetric di- and trialkylphosphites, derivatives of (-)-borneol, (-)-menthol and (-)-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose, were studied as starting reagents for the preparation of chiral organophosphorus compounds. The reaction occurs by asymmetric induction at the alpha-carbon atom of substituted alpha-alkylphosphonates. The stereoselectivity of the reaction depends on the structure of the starting compounds and the reaction conditions. The configuration of the alkylphosphonates was established by NMR spectroscopy, by transformation into alpha-hydroxyalkylphosphonic acids and by X-ray crystal structure analysis. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Organic catalysis of phospha-aldol condensation
  作者：A. O. Kolodyazhnaya、V. P. Kukhar、O. I. Kolodyazhnyi

  DOI：10.1134/s1070363208110091

  日期：2008.11

  Phospha-aldol reaction of dialkylphosphites with carbonyl compounds is catalyzed by cinchonine alkaloids and thier modified derivatives to give optically active hydroxyphosphonates. The use of diastereomeric pairs of alkaloids allowed obtaining both optical antipodes of hydroxyphosphonates. Cinchonine alkaloids show the highest enantioselectivity as organic catalysts. It was found that ordinary crystallization of some enantiomerically enriched hydroxyphosphonates leads to isolation of the enantiomerically pure stereoisomers. Hydroxyphosphonic acids were obtained by hydrolysis of phosphonates. Fluoroalkylphosphonates were obtained by reaction with diethylaminotrifluorosulfurane (DAST).
• New method for the asymmetric hydroboration of ketophosphonates and the synthesis of phospho-carnitine
  作者：Vitaly V. Nesterov、Oleg I. Kolodiazhnyi

  DOI：10.1016/j.tetasy.2006.03.025

  日期：2006.4

  The reduction of alpha- or beta-ketophosphonates with a chiral reactant 1, prepared from sodium borohydride and (R)- or (S)-tartaric acids, led to the formation of both (S)- and (R)-alpha- or beta-hydroxyphosphonates in high yields. The stereoselectivity of the reaction depended on the absolute configurations of 1 and the ketophosphonates. The reduction of di(1R,2S,5R)-menthyl ketophosphonates with (R)-1 proceeded with matched double asymmetric induction to give high diastereomeric excesses of hydroxyphosphonates (up to 96% de). This methodology was used for the preparation of enantiomerically pure phosphonate modified carnitine on a multigram scale. (c) 2006 Elsevier Ltd. All rights reserved.