(R)-(+)-(1-羟基-3-苯基-2E-丙烯基)膦酸二甲酯 | 162681-26-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 中文名称: (R)-(+)-(1-羟基-3-苯基-2E-丙烯基)膦酸二甲酯
• 英文名称: (1R)(2E)-dimethyl [1-hydroxy-3-phenyl-2-propenyl] phosphonate
• 英文别名: (E,1R)-1-dimethoxyphosphoryl-3-phenylprop-2-en-1-ol
• CAS: 162681-26-7
• 化学式: C₁₁H₁₅O₄P
• 分子量: 242.211
• InChiKey: HWNZVTWKEWAILK-ANYFNZRUSA-N

物化性质

• 沸点：
  395.4±42.0 °C(Predicted)
• 密度：
  1.222±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  (R)-(+)-(1-羟基-3-苯基-2E-丙烯基)膦酸二甲酯 在 二(氰基苯)二氯化钯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 dimethyl (3-trichloroacetamido-3-phenyl-1-propenyl) phosphonate
  参考文献：
  名称：

  烯丙基羟基膦酸酯：多功能手性构件

  摘要：

  使用一系列钯催化的反应，将烯丙基羟基膦酸酯转化为β和γ取代的氨基膦酸酯。氮亲核试剂和钯催化剂的明智选择可以实现出色的区域和立体化学控制。钯（0）催化的胺加成或甲苯磺酸氨基甲酸酯重排产生γ-取代的膦酸酯，而甲苯磺酸氨基甲酸酯与钯（II）和碱的反应产生恶唑烷酮（β-取代）。

  DOI：

  10.1016/j.jorganchem.2004.11.019
• 作为产物：
  描述：

  dimethyl (1-acetoxy-3-phenyl-2E-propenyl) phosphonate 在 Pseudomonas sp. lipase 作用下， 以 phosphate buffer 为溶剂， 以68%的产率得到(R)-(+)-(1-羟基-3-苯基-2E-丙烯基)膦酸二甲酯
  参考文献：
  名称：

  The synthesis of 1-hydroxy phosphonates of high enantiomeric excess using sequential asymmetric reactions: titanium alkoxide-catalyzed PC bond formation and kinetic resolution

  摘要：

  Titanium alkoxide-catalyzed asymmetric phosphonylation of aldehydes yields hydroxy phosphonates in moderate to good enantiomeric excess (e.e.s similar to 70%). The hydroxy phosphonates were acetylated and the acetates were subjected to enzyme-catalyzed kinetic resolution. The non-racemic acetates 2 (predominantly (R)-enantiomer) were hydrolyzed with an (R)-enantiomer-selective lipase, resulting predominantly in the hydrolysis of the (R)-isomer (at 85% conversion) to give the alcohols 3 with high e.e. Alternatively, hydrolysis of the minor enantiomeric (S)-acetate to approximately 20% conversion left the enriched (R)-configured acetate with improved e.e. (> 90%). The moderate enantio selectivities obtained in the catalytic P-C bond formation are enhanced during the enzymatic hydrolysis. Furthermore, availability of the non-racemic phosphonates permits the use of less selective enzymes, resulting in higher yields in comparison with the standard resolution of racemic materials. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00303-2

文献信息

• [5.5]-<i>P</i>-Spirocyclic Chiral Triaminoiminophosphorane-Catalyzed Asymmetric Hydrophosphonylation of Aldehydes and Ynones
  作者：Daisuke Uraguchi、Takaki Ito、Yuto Kimura、Yumiko Nobori、Makoto Sato、Takashi Ooi

  DOI：10.1246/bcsj.20170040

  日期：2017.5.15

  Development of highly efficient and enantioselective hydrophosphonylations of aldehydes and ynones mediated by [5.5]-P-spirocyclic chiral triaminoiminophosphoranes as base catalysts is described. T...

  描述了由 [5.5]-P-螺环手性三氨基亚氨基正膦作为碱催化剂介导的醛和炔酮的高效和对映选择性氢膦酰化的开发。天...
• The enantioselective addition of dialkylphosphites to aldehydes: Catalysis by a lanthanum binaphthoxide complex
  作者：Nigam P. Rath、Christopher D. Spilling

  DOI：10.1016/s0040-4039(00)76517-8

  日期：1994.1

  The enantioselective addition of dialkylphosphites to aldehydes was catalyzed by a lanthanum (R)-binaphthoxide complex to give (S)-hydroxy phosphonates in good yield and modest enantioselectivity.

  用镧（R）-联萘氧化物络合物催化亚磷酸二烷基酯对醛的对映选择性加成，以高收率和适度的对映选择性得到（S）-羟基膦酸酯。
• Synthesis of Cyclopentenones via Intramolecular HWE and the Palladium-Catalyzed Reactions of Allylic Hydroxy Phosphonate Derivatives
  作者：Bingli Yan、Christopher D. Spilling

  DOI：10.1021/jo8004028

  日期：2008.7.1

  Palladium-catalyzed decarboxylative rearrangement of nonracemic phosphono allylic acetoacetates, or the intermolecular allylic substitution of nonracemic phosphono allylic carbonates with tert-butyl acetoacetate followed by hydrolysis and decarboxylation, gave ω-ketovinyl phosphonates. A highly regioselective Wacker oxidation gave the ω,β-diketophosphonates which underwent intramolecular HWE reaction

  非外消旋膦酰基烯丙基乙酰乙酸的钯催化脱羧重排，或非乙酸膦酰基烯丙基碳酸酯的分子间烯丙基取代为乙酰乙酸叔丁酯，随后水解和脱羧，得到ω-酮乙烯基膦酸酯。高度区域选择性的Wacker氧化产生了ω，β-二酮膦酸酯，使其经历分子内HWE反应以生成非外消旋的环戊烯酮。导致膦酰基环戊烯酮的醛醇缩合与HWE反应竞争。环戊烯酮的立体化学和HWE与醛醇产物的比例取决于反应中所用碱的选择。
• Synthesis of an Optically Active Al(salalen) Complex and Its Application to Catalytic Hydrophosphonylation of Aldehydes and Aldimines
  作者：Bunnai Saito、Hiromichi Egami、Tsutomu Katsuki

  DOI：10.1021/ja0651005

  日期：2007.2.1

  serve as an efficient catalyst for hydrophosphonylation of aldehydes and aldimines, giving the corresponding alpha-hydroxy and alpha-amino phosphonates with high enantioselectivity, respectively. The scope of the hydrophosphonylation was wide, and both aliphatic and aromatic aldehydes and aldimines were successfully used as substrates for the reaction. The potent catalysis of the complex is attributed to

  以模块化合成方式新合成了光学活性铝（salalen）配合物2，发现它可作为醛和醛亚胺氢膦酰化的有效催化剂，分别得到相应的具有高对映选择性的α-羟基和α-氨基膦酸酯. 氢膦酰化的范围很广，脂肪族和芳香族醛和醛亚胺都成功地用作反应的底物。该复合物的强大催化作用归因于其独特的结构：它采用扭曲的三角双锥体构型，这使得 salalen 配体呈顺式-β 样结构，其中手性氨基位于靠近金属中心的位置。
• Stereospecific Pd(O)-Catalyzed Malonate Additions to Allylic Hydroxy Phosphonate Derivatives:  A Formal Synthesis of (−)-Enterolactone
  作者：Bingli Yan、Christopher D. Spilling

  DOI：10.1021/jo035795h

  日期：2004.4.1

  A combination of cross-metathesis and malonate addition was applied to a formal synthesis of the mammalian lignan enterolactone 5. The cross-metathesis of alkene 6 and phosphonate 3a gave the substituted allylic phosphonate 3d. The palladium-catalyzed addition of malonate 10d to the allylic phosphonate 3d was stereospecific and highly regioselective and yielded the vinyl phosphonate 11d. The vinyl

  交叉复分解和丙二酸酯添加的组合应用于哺乳动物木脂体肠内酯5的正式合成。烯烃6和膦酸酯3a的交叉复分解得到取代的烯丙基膦酸酯3d。钯催化的丙二酸酯10d向烯丙基膦酸酯3d的加成是立体特异性的，且具有高度区域选择性，并生成乙烯基膦酸酯11d。膦酸乙烯基酯11d分两步转化为内酯14，内酯14是肠内酯5合成中已知的中间体。