rac-(E)-dimethyl 2-[1,3-bis(3-bromophenyl)allyl]malonate | 1445949-52-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: rac-(E)-dimethyl 2-[1,3-bis(3-bromophenyl)allyl]malonate
• 英文别名: (E)-dimethyl 2-(1,3-bis(3-bromophenyl)allyl)malonate；dimethyl 2-[(E)-1,3-bis(3-bromophenyl)prop-2-enyl]propanedioate
• CAS: 1445949-52-9
• 化学式: C₂₀H₁₈Br₂O₄
• 分子量: 482.169
• InChiKey: FUNMZUIWLDSMJR-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  rac-(E)-1,3-bis(3-bromophenyl)-2-propen-1-yl acetate 、 丙二酸二甲酯 在 N,O-双三甲硅基乙酰胺 、 bis(η3-allyl-μ-chloropalladium(II)) 、 potassium acetate 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 生成 rac-(E)-dimethyl 2-[1,3-bis(3-bromophenyl)allyl]malonate
  参考文献：
  名称：

  使用酒石酸盐衍生的生物恶唑啉配体对乙酸烯丙酯进行高度对映选择性烷基化

  摘要：

  酒石酸盐衍生的生物恶唑啉配体与金属形成五元螯合环，被评估用于各种对称和不对称乙酸烯丙酯的不对称烯丙基烷基化 (AAA) 反应。通过使用对称和不对称的乙酸烯丙酯均实现了优异的对映选择性。

  DOI：

  10.1002/ejoc.201301208

文献信息

• Highly Enantioselective Alkylation of Allyl Acetates Using Tartrate-Derived Bioxazoline Ligands
  作者：Samydurai Jayakumar、Muthuraj Prakash、Kaluvu Balaraman、Venkitasamy Kesavan

  DOI：10.1002/ejoc.201301208

  日期：2014.1

  Tartrate-derived bioxazoline ligands, which form a five-membered chelate ring with metals, were evaluated for use in the asymmetric allylic alkylation (AAA) reactions of various symmetrical and unsymmetrical allyl acetates. Excellent enantioselectivities were achieved by using both symmetrical and unsymmetrical allyl acetates.

  酒石酸盐衍生的生物恶唑啉配体与金属形成五元螯合环，被评估用于各种对称和不对称乙酸烯丙酯的不对称烯丙基烷基化 (AAA) 反应。通过使用对称和不对称的乙酸烯丙酯均实现了优异的对映选择性。
• Efficient novel 1,2-diphosphite ligands derived from d-mannitol in the Pd-catalyzed asymmetric allylic alkylation
  作者：Ai-ping Xing、Zeng-bo Pang、Hai-feng Li、Lai-lai Wang

  DOI：10.1016/j.tet.2014.10.011

  日期：2014.11

  A novel Pd/1,2-diphosphite catalyzed asymmetric allylic alkylation of 1,3-diarylpropenyl acetate with malonates was developed. Catalyst optimization via a variation in the protecting groups at the 1,2- and/or 5,6-positions of D-mannitol skeleton and in biaryl moieties of the ligands led to a 'lead' catalyst, which efficiently mediated the allylic alkylations. The activities and enantioselectivities of the reaction clearly showed that the stereogenic centers of the skeleton and the axially chiral diaryl moieties of the ligands had a synergic effect. The ligand 1,2:5,6-di-O-isopropylidene-3,4-bis[(5)-1,1'-binaphthyl-2,2'-diyl]phosphite-D-mannitol afforded excellent yields (up to 99%) and high levels of enantioselectivies (ee up to 98%) in 1,4-dioxane/CH2Cl2 mixture (v/v, 1:1) using [Pd(pi-allyl)Cl](2) as catalytic precursor and LiOAc as base. Dramatic changes in the sense and in the degree of the enantioselectivity depending on the configuration of the diaryl moieties of the ligands and reaction conditions were observed. (C) 2014 Elsevier Ltd. All rights reserved.