[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-di(propan-2-yloxy)phosphorylacetate | 113368-90-4

• 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: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-di(propan-2-yloxy)phosphorylacetate
• CAS: 113368-90-4
• 化学式: C₂₄H₃₉O₅P
• 分子量: 438.544
• InChiKey: HQKQGLINECDNCS-CEMLEFRQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-di(propan-2-yloxy)phosphorylacetate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 甲苯 为溶剂， 反应 0.5h， 生成 (E)-(4R,7S)-4,8-bis(2,2-dimethylpropionyloxy)-7-hydroxyocta-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester
  参考文献：
  名称：

  一种通用的立体控制方法，通过使用顺序不对称的霍纳-沃兹沃思-埃蒙斯和闭环反应来制备手性四氢呋喃和四氢吡喃衍生物。

  摘要：

  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。

  DOI：

  10.1021/jo0259111
• 作为产物：
  描述：

  diisopropyl (methoxycarbonylmethyl)phosphonate 、 (-)-8-苯基薄荷醇 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 反应 120.0h， 以94%的产率得到[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-di(propan-2-yloxy)phosphorylacetate
  参考文献：
  名称：

  膦酰基乙酸酯的有效酯交换反应

  摘要：

  已开发出一种使用4-DMAP催化的酯交换反应制备差异取代的膦酰基乙酸酯和膦酰基乙酰胺的新方法。

  DOI：

  10.1016/s0040-4039(00)96188-4

文献信息

• 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。
• Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with <i>meso</i>-Dialdehydes
  作者：Joshua S. Tullis、Lauri Vares、Nina Kann、Per-Ola Norrby、Tobias Rein

  DOI：10.1021/jo981102z

  日期：1998.11.1

  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.
• 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：——
• Rein, Tobias; Kreuder, Reinhard; Zezschwitz, Paultheo von, Angewandte Chemie, 1995, vol. 107, # 9, p. 1099 - 1102
  作者：Rein, Tobias、Kreuder, Reinhard、Zezschwitz, Paultheo von、Wulff, Christian、Reiser, Oliver

  DOI：——

  日期：——