diethyl 2-(1,3-bis(4-bromophenyl)allyl)malonate | 1374010-19-1

• 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: diethyl 2-(1,3-bis(4-bromophenyl)allyl)malonate
• 英文别名: (E)-diethyl 2-(1,3-bis(4-bromophenyl)allyl)malonate；diethyl 2-[(1S,2E)-1,3-bis(4-bromophenyl)-2-propen-1-yl]malonate；diethyl 2-[(E,1S)-1,3-bis(4-bromophenyl)prop-2-enyl]propanedioate
• CAS: 1374010-19-1
• 化学式: C₂₂H₂₂Br₂O₄
• 分子量: 510.222
• InChiKey: JKCXKKKBHZHUFJ-NNJXQSOLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  丙二酸二乙酯 、 (E)-1,3-bis(4-bromophenyl)allyl acetate 在 N,O-双三甲硅基乙酰胺 、 bis(η3-allyl-μ-chloropalladium(II)) 、 (11bR,11'bR)-4,4'-[[(1R,2R)-1,2-Bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-1,2-ethanediyl]bis(oxy)]bis[dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin] 、 lithium acetate 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 4.0h， 以96%的产率得到diethyl 2-(1,3-bis(4-bromophenyl)allyl)malonate
  参考文献：
  名称：

  Efficient novel 1,2-diphosphite ligands derived from d-mannitol in the Pd-catalyzed asymmetric allylic alkylation

  摘要：

  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.

  DOI：

  10.1016/j.tet.2014.10.011

文献信息

• The synthesis of phosphine oxide-linked bis(oxazoline) ligands and their application in asymmetric allylic alkylation
  作者：Yu Jin、Da-Ming Du

  DOI：10.1016/j.tet.2012.02.078

  日期：2012.5

  The phosphine oxide-linked bis(oxazoline) ligands were designed and synthesized in two ways. One is the coupling of Grignard reagent derived from 2-(2-bromophenyl)oxazoline with phenylphosphonic dichloride, another route is the condensation of bis(2-formylphenyl)(phenyl)phosphine oxide with chiral amino alcohols followed by NBS oxidation. These new bis(oxazoline) ligands were applied in Pd-catalyzed

  设计和合成氧化膦连接的双（恶唑啉）配体。一种是衍生自2-（2-溴苯基）恶唑啉的格氏试剂与苯基二氯膦偶联，另一种途径是将双（2-甲酰基苯基）（苯基）膦氧化物与手性氨基醇缩合，然后进行NBS氧化。这些新的双（恶唑啉）配体用于钯催化的不对称烯丙基烷基化反应中，并用二苯基取代的配体（高达95％ee）获得了良好的收率和对映选择性。
• Synthesis and application of a new hexamethyl-1,1′-spirobiindane-based chiral bisphosphine (HMSI-PHOS) ligand in asymmetric allylic alkylation
  作者：Shirui Chang、Lei Wang、Xufeng Lin

  DOI：10.1039/c8ob00279g

  日期：——

  The emerging and versatile application of chiral bisphosphine ligands in diverse asymmetric reactions has resulted in great demand for novel bisphosphine ligands containing different innovative backbones. Herein, a new type of chiral spiro bisphosphine ligand (HMSI-PHOS) has been developed on the basis of a hexamethyl-1,1′-spirobiindane motif. A series of new HMSI-PHOS ligands were synthesized and

  手性双膦配体在各种不对称反应中的新兴和广泛应用导致对含有不同创新主链的新型双膦配体的巨大需求。在此，基于六甲基-1，1'-螺双茚满基序，开发了新型的手性螺双膦配体（HMSI-PHOS）。合成了一系列新的HMSI-PHOS配体，并将其用于Pd催化的不对称烯丙基烷基化反应中，并用苯基取代的配体获得了中等至良好的收率和对映选择性。
• Catalytic activity of chiral chelating <i>N</i>-heterocyclic carbene palladium complexes towards asymmetric allylic alkylation
  作者：Liangru Yang、Yunfei Li、Pu Mao、Jinwei Yuan、Yongmei Xiao

  DOI：10.1080/10426507.2018.1546177

  日期：2019.8.3

  Abstract The catalytic activity of a series of chiral heteroaryl coordinated chelating N-heterocyclic carbene (NHC) palladium complexes towards asymmetric allylic alkylation (AAA) were presented here. The effects of different N-substituents, NHC backbones and chelate rings on the catalytic activity and the enantioselectivity of the alkylation of (E)-1,3-diarylallyl acetates with dialkyl malonate were

  摘要 本文介绍了一系列手性杂芳基配位螯合 N-杂环卡宾 (NHC) 钯配合物对不对称烯丙基烷基化 (AAA) 的催化活性。研究了不同N-取代基、NHC主链和螯合环对(E)-1,3-二芳基烯丙酯乙酸酯与丙二酸二烷基酯烷基化的催化活性和对映选择性的影响。结果表明，在优化条件下，带有吡啶基配位五元螯合环的配合物3a、3b和3i表现出较高的催化活性和手性诱导效率。以高收率和中等ee值获得相应的烷基化产物。此外，发现(E)-1,3-二芳基烯丙基乙酸酯的取代基和亲核试剂的类型也影响结果。
• 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.