(E)-diethyl (2-methyl-3-phenylallyl) phosphate | 1005414-33-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (E)-diethyl (2-methyl-3-phenylallyl) phosphate
• 英文别名: (E)-2-methyl-3-phenylallyl diethyl phosphate；diethyl [(E)-2-methyl-3-phenylprop-2-enyl] phosphate
• CAS: 1005414-33-4
• 化学式: C₁₄H₂₁O₄P
• 分子量: 284.292
• InChiKey: IKJANFLCVNPCKX-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-diethyl (2-methyl-3-phenylallyl) phosphate 、 N-(2-methylbenzoyl)-8-aminoquinoline 在 bis(1,5-cyclooctadiene)nickel (0) 、 sodium carbonate 、 三环己基膦 作用下， 以 甲苯 为溶剂， 反应 30.0h， 以98%的产率得到(E)-2-methyl-6-(2-methyl-3-phenylallyl)-N-(quinolin-8-yl)benzamide
  参考文献：
  名称：

  镍催化磷酸与烯丙基磷酸盐的偶联：现场选择合成路线到线性烯丙基芳烃

  摘要：

  据报道，镍/膦催化剂可以使C–H烯丙基化有效地进行，而烯丙基位点的选择性主要受空间效应的支配。该反应提供了从容易获得的苯甲酰胺和磷酸烯丙基酯选择性制备线性烯丙基芳烃的简便且可预测的途径。

  DOI：

  10.1021/ol501707z
• 作为产物：
  描述：

  亚磷酸二乙酯 、 反式-alpha-甲基肉桂醛 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 4.03h， 以73%的产率得到(E)-diethyl (2-methyl-3-phenylallyl) phosphate
  参考文献：
  名称：

  BuLi-triggered phospha-Brook rearrangement: efficient synthesis of organophosphates from ketones and aldehydes

  摘要：

  A variety of organophosphates are synthesized from n-BuLi-triggered, (additional) solvent-free reactions of diethyl phosphite with both activated/unactivated ketones and aldehydes preferably at room temperature via phospha-Brook rearrangement. We could successfully synthesize the naphthylic/allylic phosphates using this approach. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.04.073

文献信息

• Asymmetric Catalysis with Silicon-Based Cuprates: Enantio- and Regioselective Allylic Substitution of Linear Precursors
  作者：Alexander Hensel、Martin Oestreich

  DOI：10.1002/chem.201501371

  日期：2015.6.15

  linear allylic phosphates that makes use of catalytically generated cuprate‐type silicon nucleophiles is reported. The method relies on soft bis(triorganosilyl) zincs as silicon pronucleophiles that are prepared in situ from the corresponding hard lithium reagents by transmetalation with ZnCl2. With a preformed chiral N‐heterocyclic carbene–copper(I) complex as catalyst, exceedingly high enantiomeric excesses

  据报道，利用催化生成的铜酸盐型硅亲核试剂，对线性和烯丙基磷酸的对映体和区域选择性烯丙基甲硅烷基化。该方法依赖于软双（三有机甲硅烷基）锌作为硅原核亲核体，其是通过与相应的硬锂试剂通过用ZnCl 2进行金属转移而原位制备的。用预先形成的手性N-杂环卡宾-铜（I）络合物作为催化剂，可获得极高的对映体过量。新方法优于使用硅硼试剂作为亲核硅来源的现有方法。
• Asymmetric Synthesis of α-Chiral Allylic Silanes by Enantioconvergent γ-Selective Copper(I)-Catalyzed Allylic Silylation
  作者：Lukas B. Delvos、Devendra J. Vyas、Martin Oestreich

  DOI：10.1002/anie.201300648

  日期：2013.4.22

  way: Regio‐ and enantioselective allylic substitution with a silicon nucleophile generated by copper(I)‐catalyzed SiB bond activation provides direct access to α‐chiral allylic silanes from linear acceptors. The enantioconvergent catalysis employing McQuade's six‐membered N‐heterocyclic‐carbene–copper(I) catalyst is applicable to aryl‐ and alkyl‐substituted allylic phosphates (see scheme).

  γ方式：由铜（I）催化的SiB键活化产生的硅亲核试剂对区域和对映体选择性烯丙基取代可从线性受体直接进入α-手性烯丙基硅烷。使用McQuade的六元N-杂环卡宾-铜（I）催化剂的对映体收敛催化作用适用于芳基和烷基取代的烯丙基磷酸酯（参见方案）。
• Highly Site- and Enantioselective Cu-Catalyzed Allylic Alkylation Reactions with Easily Accessible Vinylaluminum Reagents
  作者：Yunmi Lee、Katsuhiro Akiyama、Dennis G. Gillingham、M. Kevin Brown、Amir H. Hoveyda

  DOI：10.1021/ja0782192

  日期：2008.1.1

  An efficient method for catalytic asymmetric allylic alkylation (AAA) of allylic phosphates with vinylaluminum reagents is reported. The vinylmetal reagents are prepared by reaction of commercially available DIBAL-H and a terminal alkyne. The resulting vinylaluminum reagent can be used directy, without isolation or purification. AAA reactions are promoted in the presence of 0.5-2.5 mol % of a readily available chiral N-heterocyclic carbene (NHC) complex and 1-5 mol % commercially available and air stable Cu salt (CUCl2-2H(2)O). The desired products are typically obtained within 2-12 h in 74% to 95% isolated yield, 77% to >98% ee, and in >98% E selectivity: >98% S(N)2' selectively is obtained in all but one instance (90%). The hydroalummation/catalytic AAA sequence can be performed in a single vessel, on gram scale.
• Nickel-Catalyzed C–H Coupling with Allyl Phosphates: A Site-Selective Synthetic Route to Linear Allylarenes
  作者：Xuefeng Cong、Yuexuan Li、Yu Wei、Xiaoming Zeng

  DOI：10.1021/ol501707z

  日期：2014.8.1

  reported that a nickel/phosphine catalyst allows the C–H allylation to occur effectively with the allyl site selectivity predominantly governed by steric effects. This reaction provides a facile and predictable route for the selective preparation of linear allylarenes from readily available benzamides and allyl phosphates.

  据报道，镍/膦催化剂可以使C–H烯丙基化有效地进行，而烯丙基位点的选择性主要受空间效应的支配。该反应提供了从容易获得的苯甲酰胺和磷酸烯丙基酯选择性制备线性烯丙基芳烃的简便且可预测的途径。
• BuLi-triggered phospha-Brook rearrangement: efficient synthesis of organophosphates from ketones and aldehydes
  作者：Gangaram Pallikonda、Ranga Santosh、Subhas Ghosal、Manab Chakravarty

  DOI：10.1016/j.tetlet.2015.04.073

  日期：2015.6

  A variety of organophosphates are synthesized from n-BuLi-triggered, (additional) solvent-free reactions of diethyl phosphite with both activated/unactivated ketones and aldehydes preferably at room temperature via phospha-Brook rearrangement. We could successfully synthesize the naphthylic/allylic phosphates using this approach. (C) 2015 Elsevier Ltd. All rights reserved.