hydrogen di[(1R,2S,5R)-menthyl] phosphite | 211183-18-5

• 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: hydrogen di[(1R,2S,5R)-menthyl] phosphite
• 英文别名: di-(1R,2S,5R)-menthyl phosphite；(-)-dimenthyl phosphite；(1R,2S,5R)-dimenthyl phosphite；(1S,2R,4R)-4-methyl-2-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxyphosphonoyloxy-1-propan-2-ylcyclohexane
• CAS: 211183-18-5
• 化学式: C₂₀H₃₉O₃P
• 分子量: 358.502
• InChiKey: IHZIXDJGEOIMAS-XRNRSJMDSA-N

物化性质

• 沸点：
  428.2±12.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  hydrogen di[(1R,2S,5R)-menthyl] phosphite 在 劳森试剂 作用下， 以95%的产率得到O,O-dimenthyl thiophosphite
  参考文献：
  名称：

  Radical addition reactions of chiral phosphorus hydrides

  摘要：

  Intermolecular radical addition of a (1R,2R,3S,5R)-(-)-pinanediol-derived thiophosphite leads to the diastereoselective formation of organophosphorus adducts. Addition of the intermediate phosphonothioyl radical to electron-rich alkenes or alkynes occurs with retention of configuration at phosphorus. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.04.001
• 作为产物：
  描述：

  (1S,2R,4R)-2-[chloro-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxyphosphoryl]oxy-4-methyl-1-propan-2-ylcyclohexane 在 水 作用下， 生成 hydrogen di[(1R,2S,5R)-menthyl] phosphite
  参考文献：
  名称：

  Sigmatropic [2,3]-Wittig Rearrangement of α-Allylic-Heterosubstituted Methylphosphonates. Part 31: High Diastereoselectivity in the Rearrangement of Anion of Dimenthyl Allyloxymethylphosphonate

  摘要：

  DOI：

  10.1016/00404-0399(50)1353j-

文献信息

• Copper-mediated cross-coupling of 1,1-dibromo-1-alkenes with dialkyl phosphites: a convenient synthesis of 1-alkenylphosphonates
  作者：Gwilherm Evano、Krishnaji Tadiparthi、François Couty

  DOI：10.1039/c0cc01617a

  日期：——

  An efficient and stereoselective procedure for the preparation of E-1-alkenylphosphonates by copper-mediated cross-coupling between 1,1-dibromo-1-alkenes and dialkyl phosphites is reported. The reaction allows for formal substitution of both bromine atoms, respectively, by an hydrogen and a dialkoxyphosphoryl.

  报道了一种通过铜介导的1，1-二溴-1-烯与亚磷酸二烷基酯的交叉偶联制备E-1-烯基膦酸酯的有效和立体选择性的方法。该反应允许两个溴原子分别被氢和二烷氧基磷酰基正式取代。
• Enantiomeric O,O-dimenthyl α-iminotrifluoroethylphosphonates: Novel chiral building blocks in asymmetric synthesis of α-trifluoromethylated α-aminophosphonic acid derivatives
  作者：Yuliya V. Rassukana、Oleg V. Stanko、Petro P. Onys’ko

  DOI：10.1016/j.jfluchem.2019.01.007

  日期：2019.3

  Based on reaction of (+)- or (-)-dimenthyl phosphite with trifluoroacetonitrile the synthesis of optically active O,O-dimenthyl α-iminotrifluoroethylphosphonates was developed. The synthetic potential of these novel chiral synthons was demonstrated by their easy diastereoselective functionalization (hydrogenation, proline-catalyzed Mannich reaction with acetone, aza-Henry reaction, aminoalkylation

  基于（+）-或（-）-二薄荷基亚磷酸酯与三氟乙腈的反应，开发了光学活性的O，O-二薄荷基α-亚氨基三氟乙基膦酸酯。这些新型手性合成子的合成潜力通过其非对映选择性官能化（加氢，脯氨酸催化的曼尼希与丙酮的反应，氮杂亨利反应，富电子杂环的氨基烷基化）得到了具有生物相关性的光学活性化合物（α-三氟甲基- α-氨基）甲基膦酰基残基。
• Copper-Mediated Selective Cross-Coupling of 1,1-Dibromo-1-alkenes and Heteronucleophiles: Development of General Routes to Heterosubstituted Alkynes and Alkenes
  作者：Kévin Jouvin、Alexis Coste、Alexandre Bayle、Frédéric Legrand、Ganesan Karthikeyan、Krishnaji Tadiparthi、Gwilherm Evano

  DOI：10.1021/om3005614

  日期：2012.11.26

  site-selective, double, or alkynylative cross-coupling, therefore providing divergent and straightforward entries to numerous building blocks such as bromoenamides, ynamides, ketene N,N-acetals, bromoenol ethers, ynol ethers, ketene O,O-acetals, or vinylphosphonates and further expanding the copper catalysis toolbox with useful and versatile processes.

  据报道，有效的和通用的程序是将1，1-二溴代烯烃与N-，O-和P-亲核试剂进行交叉偶联。反应条件的微调允许位点选择性，双重或炔基交叉偶联，因此为许多结构单元（如溴酰胺，乙酰胺，乙烯酮N，N-乙缩醛，溴烯醇醚，炔醇醚）提供了分散而直接的入口，乙烯酮O，O-乙缩醛或乙烯基膦酸酯，并通过有用的通用方法进一步扩展了铜催化工具箱。
• Organophosphorus Chemistry without PCl₃: A Bridge from Hypophosphorous Acid to H-Phosphonate Diesters
  作者：Henry C. Fisher、Lucie Prost、Jean-Luc Montchamp

  DOI：10.1002/ejoc.201301412

  日期：2013.12

  A process for the conversion of hypophosphorous acid (H3PO2, HPA) and alcohols into various H-phosphonate diesters [(RO)2P(O)H] is described. The new reaction provides a missing bridge between HPA and important H-phosphonates, completely avoiding the use of PCl3. Nickel chloride or nickel on silica catalyze the oxidative phosphorylation of alkyl phosphinates with various alcohols or water. The reaction

  描述了将次磷酸 (H3PO2, HPA) 和醇转化为各种 H-膦酸二酯 [(RO)2P(O)H] 的过程。新反应在 HPA 和重要的 H-膦酸盐之间提供了一个缺失的桥梁，完全避免了 PCl3 的使用。氯化镍或二氧化硅上的镍催化烷基次膦酸盐与各种醇或水的氧化磷酸化。该反应是原子经济的，避免了废物的形成。完全避免了以前对氯和碱的需求。
• Electrocatalytic C–H phosphorylation through nickel(III/IV/II) catalysis
  作者：Shou-Kun Zhang、Antonio Del Vecchio、Rositha Kuniyil、Antonis M. Messinis、Zhipeng Lin、Lutz Ackermann

  DOI：10.1016/j.chempr.2021.04.009

  日期：2021.5

  relevant nickel(II) and nickel(III) intermediates were isolated and fully characterized by X-ray diffraction analysis. Catalytically relevant nickel complexes were observed by in operando high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) monitoring. Cyclic voltammetry analysis and density functional theory (DFT) calculations provided strong evidence for a nickel(III/IV/II) manifold.

  CH-H磷酸化是通过使用无废电作为氧化还原替代物的富含地球的镍催化剂实现的。芳烃，杂芳烃和烯烃与各种膦酸酯化试剂的强健的镍氢电氧化CH活化作用，成功递送了与生物活性化合物和材料相关的芳基膦酸酯，苯基膦氧化物和二氮杂磷腈氧化物。胍辅助电氧化C-P的形成避免了以分子氢为唯一副产物的化学氧化剂。分离了具有催化作用的镍（II）和镍（III）中间体，并通过X射线衍射分析对其进行了全面表征。在操作中观察到了催化相关的镍配合物高分辨率电喷雾电离质谱（HR-ESI-MS）监控。循环伏安分析和密度泛函理论（DFT）计算为镍（III / IV / II）歧管提供了有力的证据。