(+)-(R)-1-phenyl-1-hydroxymethylphosphonic acid | 104944-25-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(R)-1-phenyl-1-hydroxymethylphosphonic acid
• 英文别名: (R)-(+)-α-hydroxybenzylphosphonic acid；(R)-(+)-hydroxy(phenyl)methanephosphonic acid；(R)-1-phenyl-1-hydroxymethylphosphonic acid；(R)-α-hydroxybenzylphosphonic acid；hydroxy(phenyl)methylphosphonic acid；[(R)-hydroxy(phenyl)methyl]phosphonic acid
• CAS: 104944-25-4
• 化学式: C₇H₉O₄P
• 分子量: 188.12
• InChiKey: YLVXPXINUWURSG-SSDOTTSWSA-N

物化性质

• 熔点：
  226 °C
• 沸点：
  434.0±55.0 °C(Predicted)
• 密度：
  1.527±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(R)-1-phenyl-1-hydroxymethylphosphonic acid 、 (Z)-benzyl N,N'-dicyclohexylcarbamimidate 以 苯 为溶剂， 反应 4.0h， 以75%的产率得到Phosphonic acid, (hydroxyphenylmethyl)-, bis(phenylmethyl) ester, (R)-
  参考文献：
  名称：

  A Simple, Efficient Synthesis of Dibenzyl and Di-p-nitrobenzyl 1-Hydroxyalkanephosphonates

  摘要：

  二苯基和二对硝基苯基1-羟基烷基磷酸酯3a-i是通过将1-羟基烷基磷酸一酸1与O-苄基和O-(对硝基苯基)-N,N′-二环己基异脲2进行烷基化反应制备的。

  DOI：

  10.1055/s-1988-33434
• 作为产物：
  描述：

  benzylphosphonic dichloride 在 吡啶 、 4-二甲氨基吡啶 、 四(三苯基膦)钯 、 (-)-8,8-(dichlorocamphor)sulfonyloxaziridine 、 sodium hexamethyldisilazane 、 5,5-二甲基-1,3-环己二酮 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (+)-(R)-1-phenyl-1-hydroxymethylphosphonic acid
  参考文献：
  名称：

  Chiral, non-racemic α-hydroxyphosphonates and phosphonic acids via stereoselective hydroxylation of diallyl benzylphosphonates

  摘要：

  Chiral, non-racemic alpha-hydroxyphosphonates have been prepared in high enantiomeric excess (96-98% ee), via stereoselective oxaziridine-mediated hydroxylation of diallyl benzylphosphonates. The enantiomeric purity and absolute configuration of the alpha-hydroxyphosphonates was established from H-1 and P-31 NMR spectroscopy of the (S)-O-methylmandelate esters. Deprotection of the diallyl alpha-hydroxyphosphonates under neutral conditions furnished the corresponding free phosphonic acids, retaining a high degree of stereochemical purity (90 to >98% ee). (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00786-3

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
• 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。
• Double Asymmetric Induction as Method for the Synthesis of Chiral Organophosphorus Compounds
  作者：Oleg I. Kolodiazhnyi

  DOI：10.1080/10426500213410

  日期：2002.8

  New examples of multistereoselective syntheses of organophosphorus compounds are described.

  描述了有机磷化合物的多立体选择性合成的新实例。
• Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1021/jo00109a025

  日期：1995.2

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.