(R, E)-dimethyl 2-[1,3-bis(3-bromophenyl)allyl]malonate | 1607820-08-5

• 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: (R, E)-dimethyl 2-[1,3-bis(3-bromophenyl)allyl]malonate
• 英文别名: (E)-dimethyl 2-(1,3-bis(3-bromophenyl)allyl)malonate
• CAS: 1607820-08-5
• 化学式: C₂₀H₁₈Br₂O₄
• 分子量: 482.169
• InChiKey: FUNMZUIWLDSMJR-FVNWOWOISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.97
• 重原子数：
  26.0
• 可旋转键数：
  6.0
• 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：
  0.0
• 氢受体数：
  4.0

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)) 、 (4S,4'S)-2,2'-bis[(1S)-1-(6-methoxy-2-naphthyl)ethyl]-4,4',5,5'-tetrahydro-4,4'-bi-1,3-oxazole 、 potassium acetate 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以89%的产率得到(R, 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

• Synthesis of highly rigid phosphine–oxazoline ligands for palladium-catalyzed asymmetric allylic alkylation
  作者：Zhongxuan Qiu、Rui Sun、Dawei Teng

  DOI：10.1039/c8ob02265h

  日期：——

  A highly rigid spiro phosphine–oxazoline ligand skeleton with a spirocarbon stereogenic center was developed from 7-bromo-1-indanone. The catalytic performance of the ligand was demonstrated in palladium-catalyzed asymmetric allylic alkylation. Under optimized conditions, high yields (up to 99%) and enantioselectivities (up to 99.9% ee) were obtained for reactions of 1,3-diphenylallyl acetates and

  由7-溴-1-茚满酮开发了具有螺碳立构中心的高刚性螺膦-恶唑啉配体骨架。配体的催化性能在钯催化的不对称烯丙基烷基化反应中得到证实。在优化的条件下，对于1,3-二苯基烯丙基乙酸酯和对称的1,3-二羰基底物的反应，可获得高产率（高达99％）和对映选择性（高达99.9％ee）。
• Design of bifunctional chiral phenanthroline ligand with Lewis basic site for palladium-catalyzed asymmetric allylic substitution
  作者：Yuki Naganawa、Hiroki Abe、Hisao Nishiyama

  DOI：10.1039/c8cc00754c

  日期：——

  Conceptually new bifunctional chiral ligands were developed. The axially chiral N,N-bidentate phenanthroline ligand (S)-1 was found to be effective for Pd-catalyzed asymmetric allylic substitution of allyl acetate and dialkyl malonate. The intramolecular Lewis basic group from the hydroxybinaphthyl structure of (S)-1 played a pivotal role in the high reactivity and enantioselectivity.

  从概念上讲，开发了新的双功能手性配体。发现轴向手性N，N-二齿菲咯啉配体（S）-1对于Pd催化乙酸烯丙酯和丙二酸二烷基酯的不对称烯丙基取代是有效的。（S）-1的羟基联萘结构的分子内路易斯碱性基团在高反应性和对映选择性中起关键作用。
• 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。
• Simple chiral sulfinyl imine–thioether ligands for Pd-catalyzed allylic alkylation
  作者：Ge-Yun You、Xiao-Feng Liu、Pei-Wen Fang、Lu-Fang Liang、Cheng-Hao Dai、Bin Feng

  DOI：10.1007/s11696-022-02176-2

  日期：2022.7

  A set of chiral sulfinyl imine–thioether ligands are prepared via dehydration condensation of substituted benzaldehyde and chiral sulfinamide. The activity of these ligands in Pd-catalyzed asymmetric allylic alkylation reaction is studied, and the results indicate that the structure of sulfinamide motifs has an obvious effect on the e.r. value and yield. The chiral p-tolylsulfinamide derived ligands

  通过取代苯甲醛和手性亚磺酰胺的脱水缩合制备了一组手性亚磺酰亚胺-硫醚配体。研究了这些配体在Pd催化的不对称烯丙基烷基化反应中的活性，结果表明亚磺酰胺基序的结构对er值和产率有明显影响。手性对甲苯基亚磺酰胺衍生的配体可以有效地促进反应，而具有叔丁基的配体不能催化反应。然后，还研究了最佳反应条件下的底物范围。
• New P,N_sp3ligands for palladium-catalyzed asymmetric allylic substitutions
  作者：Qin Su、Chuan-Jin Hou、De-Quan Wei、Hao Qin、Ding-Hua Liang、Xiang-Ping Hu

  DOI：10.1039/d3ob00519d

  日期：——

  New P,Nsp3 bidentate ligands containing two chiral carbon centers were developed and applied to palladium-catalyzed asymmetric allylic substitution reactions. Good generalities with various nucleophiles, including carbon, nitrogen and oxygen containing nucleophiles, were achieved with up to 96% ee and 98% yield. This reaction provides an efficient method for the asymmetric formation of C–C, C–N and

  开发了包含两个手性碳中心的新型 P,N sp3双齿配体，并将其应用于钯催化的不对称烯丙基取代反应。与各种亲核试剂（包括含碳、含氮和含氧的亲核试剂）的良好通用性达到了高达 96% 的 ee 和 98% 的产率。该反应为C-C、C-N和C-O键的不对称形成提供了一种有效的方法。