[bis(2,2,2-trifluoroethoxy)phosphoryl]acetic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester | 155795-46-3

• 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: [bis(2,2,2-trifluoroethoxy)phosphoryl]acetic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester
• 英文别名: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-[bis(2,2,2-trifluoroethoxy)phosphoryl]acetate
• CAS: 155795-46-3
• 化学式: C₂₂H₂₉F₆O₅P
• 分子量: 518.433
• InChiKey: NEFSQBNUIAZHAI-KBAYOESNSA-N

物化性质

• 沸点：
  478.2±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  [bis(2,2,2-trifluoroethoxy)phosphoryl]acetic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester 在 18-冠醚-6 、 sodium hexamethyldisilazane 、 对甲苯磺酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 36.0h， 生成 10-benzyl 1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl] (2E,4R,8E)-4-hydroxydeca-2,8-dienedioate
  参考文献：
  名称：

  向非经典匿名产乙酸原酶的扩散。吡喃霉素和吡咯丁菌素的合成†

  摘要：

  提出了从常见的后期中间体合成非经典的非丙酮产乙酸原素，吡喃霉素和吡喃霉素。关键元素的构建依赖于不对称的HWE反应，包括内消旋异构化-二醛和消旋醛的平行动力学拆分。立体收敛的Pd催化的取代用于以不同形式的正交保护基团以受保护的形式安装C4立体中心。采用立体选择性的Zn介导的炔基化反应形成1，4-和1，6-二醇的不同策略用于完成核心结构。值得注意的是，针对吡喃霉素的立体选择性偶联反应以高度官能化的片段进行。通过2,3,6-三取代的四氢吡喃亚基的所有立体异构体的发散合成，进一步扩展了该方法。

  DOI：

  10.1021/jo052233k
• 作为产物：
  描述：

  O,O'-双(2,2,2-三氟乙基)磷乙酸甲酯 、 (-)-8-苯基薄荷醇 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 以89%的产率得到[bis(2,2,2-trifluoroethoxy)phosphoryl]acetic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester
  参考文献：
  名称：

  Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with meso-Dialdehydes

  摘要：

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.

  DOI：

  10.1021/jo981102z

文献信息

• Total Synthesis of Pyranicin
  作者：Daniel Strand、Tobias Rein

  DOI：10.1021/ol0479242

  日期：2005.1.1

  [Reaction: see text] A stereocontrolled convergent synthesis of the annonaceous acetogenin pyranicin (1) is presented. Asymmetric Horner-Wadsworth-Emmons (HWE) reactions were used to access key intermediates. The tetrahydropyran derivative 2 was obtained via an asymmetric desymmetrization of the meso-dialdehyde 6, and the butenolide fragment was constructed using a stereoconvergent reaction sequence

  [反应：见正文]提出了一种立体控制的收敛性合成壬基产乙酸原素吡喃霉素（1）。不对称的霍纳-沃兹沃思-埃蒙斯（HWE）反应用于访问关键中间体。四氢吡喃衍生物2是通过内二醛6的不对称脱对称获得的，丁烯内酯片段的构建采用了立体收敛反应序列，该过程涉及平行的动力学HWE拆分，然后进行了Pd催化的烯丙基取代。使用Carreira的不对称乙炔加成方法安装了C10 / C15 1,6-二醇基序。
• A Versatile Stereocontrolled Approach to Chiral Tetrahydrofuran and Tetrahydropyran Derivatives by Use of Sequential Asymmetric Horner−Wadsworth−Emmons and Ring-Closure Reactions
  作者：Lauri Vares、Tobias Rein

  DOI：10.1021/jo0259111

  日期：2002.10.1

  use of an asymmetric Horner-Wadsworth-Emmons reaction and a cyclization step is presented. The approach is both stereochemically and structurally versatile since three different cyclization methods can be employed starting from the same HWE product: (i) palladium-catalyzed substitution, (ii) hetero-Michael addition, or (iii) epoxide opening. The asymmetric HWE reaction controls the absolute configuration

  提出了一种基于顺序使用不对称的霍纳-沃兹沃思-埃蒙斯反应和环化步骤的手性四氢呋喃和四氢吡喃衍生物的方法。该方法在立体化学和结构上都是通用的，因为可以从相同的HWE产品开始使用三种不同的环化方法：（i）钯催化的取代，（ii）杂-迈克尔加成，或（iii）环氧开放。不对称的HWE反应控制最终产物的绝对构型，而相对构型则受HWE反应中几何选择性和相应环化方法的立体化学的综合影响控制。
• Parallel Kinetic Resolution of Racemic Aldehydes by Use of Asymmetric Horner−Wadsworth−Emmons Reactions
  作者：Torben M. Pedersen、Jakob F. Jensen、Rikke E. Humble、Tobias Rein、David Tanner、Kerstin Bodmann、Oliver Reiser

  DOI：10.1021/ol991387h

  日期：2000.2.1

  [reaction: see text] A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy allows conversion of a racemic aldehyde to two different, synthetically useful chiral

  [反应：参见正文]外消旋醛可通过与两种不同的手性膦酸酯同时反应而经历平行动力学拆分（PKR），手性助剂的结构或磷酰基的结构不同（即一个（E） -和一种（Z）选择性试剂）。与常规的动力学拆分方法相比，该策略允许将外消旋醛转化为两种不同的，合成上有用的手性产物，具有基本翻倍的材料通量和相似或改进的选择性。
• Versatile stereocontrol in kinetic resolution of a diphenylphosphinyl-protected α-amino aldehyde by reaction with chiral phosphonates
  作者：Reinhard Kreuder、Tobias Rein、Oliver Reiser

  DOI：10.1016/s0040-4039(97)10428-2

  日期：1997.12

  In kinetic resolutions of the racemic aldehyde 1 by reaction with chiral phosphonates of type 2, all of which contain the same chiral auxiliary in the same enantiomeric form, any of the four diastereomers 3a, 3b, 4a or 4b can be obtained as the main product by an appropriate choice of reaction parameters (geometric selectivities from 66:34 to 98:2, diastereomer ratios between 93:7 and greater than or equal to 99:1). The switch in stereoselectivity observed when KHMDS or NaHMDS is used as base instead of KHMDS/18-crown-6 is rationalized as resulting from a change in influence of the aldehyde alpha-stereocenter from Felkin-Anh-Eisenstein to chelation control. (C) 1997 Elsevier Science Ltd.
• Rein, Tobias; Kann, Nina; Kreuder, Reinhard, Angewandte Chemie, 1994, vol. 106, # 5, p. 597 - 599
  作者：Rein, Tobias、Kann, Nina、Kreuder, Reinhard、Gangloff, Benoit、Reiser, Oliver

  DOI：——

  日期：——