diethyl 2-methyl-2-(2-methylallyl)malonate | 78331-64-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-methyl-2-(2-methylallyl)malonate
• 英文别名: diethyl (3-butene-2-yl)methylmalonate；Diethyl 2-(but-3-en-2-yl)-2-methylmalonate；diethyl 2-but-3-en-2-yl-2-methylpropanedioate
• CAS: 78331-64-3
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: WVGMGSHVUUFGSC-UHFFFAOYSA-N

物化性质

• 沸点：
  239.3±20.0 °C(Predicted)
• 密度：
  0.996±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  1-(三氟乙酰基)-2-丁烯 生成 diethyl 2-methyl-2-(2-methylallyl)malonate
  参考文献：
  名称：

  SILVERMAN G. S.; STRICKLAND S.; NICHOLAS K. M., ORGANOMETALLICS, 5,(1986) N 10, 2117-2124

  摘要：

  DOI：

文献信息

• Deconvoluting the Memory Effect in Pd-Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride
  作者：Peter Fristrup、Thomas Jensen、Jakob Hoppe、Per-Ola Norrby

  DOI：10.1002/chem.200600152

  日期：2006.7.5

  syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which the allylic terminus originally bearing the leaving group has a higher reactivity. The latter effect, termed regioretention, can be rationalized by ionization from a palladium complex bearing a chloride ion, forming an unsymmetrically substituted [Pd(eta3-allyl)] complex. DFT calculations verify that

  对Tsuji-Trost反应中产物分布的分析表明，已报道的“记忆效应”的几种情况可归因于最初形成的顺式和反式[Pd（eta3-烯丙基）]配合物的缓慢互变。氯化物的添加触发了真正的记忆效应，其中最初带有离去基团的烯丙基末端具有更高的反应性。后者的作用称为区域保留，可以通过从带有氯离子的钯络合物中进行电离来合理化，从而形成不对称取代的[Pd（eta3-烯丙基）]络合物。DFT计算证实，在初始电离和随后的亲核攻击中，膦配体的反式位置均具有更高的反应性。
• Bulky Monodentate Phosphoramidites in Palladium-Catalyzed Allylic Alkylation Reactions: Aspects of Regioselectivity and Enantioselectivity
  作者：Maarten D. K. Boele、Paul C. J. Kamer、Martin Lutz、Anthony L. Spek、Johannes G. de Vries、Piet W. N. M. van Leeuwen、Gino P. F. van Strijdonck

  DOI：10.1002/chem.200400154

  日期：2004.12.17

  A series of bulky monodentate phosphoramidite ligands, based on biphenol, BINOL and TADDOL backbones, have been employed in the Pd-catalysed allylic alkylation reaction. Reaction of disodium diethyl 2-methyl malonate with monosubstituted allylic substrates in the presence of palladium complexes of the phosphoramidite ligands proceeds smoothly at room temperature. The regioselectivities observed depend

  基于双酚，BINOL和TADDOL主链的一系列庞大的单齿亚磷酰胺配体已用于Pd催化的烯丙基烷基化反应中。在亚磷酰胺配体的钯配合物存在下，2-甲基丙二酸二乙酯二钠与单取代的烯丙基底物的反应在室温下顺利进行。观察到的区域选择性在很大程度上取决于离去基团和烯丙基起始化合物的几何形状。当这些配体以[Pd（烯丙基）（X）]配合物（烯丙基= C3H5、1-CH3C3H4、1-C6H5C3H4、1,3-（C6H5）2C3H3; X = Cl，OAc）连接时，会发生单配位。通过[Pd（C3H5）（1）（Cl）]的X射线衍射确定的固态结构显示出烯丙基部分的非对称配位，这是由于亚磷酰胺配体相对于X-的较强反式影响所致。在所有这些配合物中，顺反异构体是溶液中存在的主要物质。由于顺式，顺式配合物的快速异构化和高反应性，烷基化后形成的主要产物是线性产物，特别是对于在卤化物抗衡离子存在下的单取代苯基烯丙基底物而言。但
• Bite angle effect of bidentate P–N ligands in palladium catalysed allylic alkylation †
  作者：Richard J. van Haaren、Cees J. M. Druijven、Gino P. F. van Strijdonck、Henk Oevering、Joost N. H. Reek、Paul C. J. Kamer、Piet W. N. M. van Leeuwen

  DOI：10.1039/b001355m

  日期：——

  Two series of new bidentate P–N ligands have been synthesized. Application of these ligands in the palladium catalysed allylic alkylation of crotyl chloride and cinnamyl chloride leads to the preferential formation of the branched product. A larger bite angle of the ligand leads to higher regioselectivity. Stoichiometric alkylation of the complex [Pd(C4H7)p-MeOC6H4CN(CH2)4OPPh2}][O3SCF3] proceeds with 88% regioselectivity to the branched product.

  合成了两系列新的双齿P–N配体。这些配体在钯催化的烯丙基氯与克罗基氯和肉桂基氯的烷基化反应中，优先形成支化产物。配体的较大咬合角度导致更高的区域选择性。复合物[Pd(C4H7)p-MeOC6H4CN(CH2)4OPPh2}][O3SCF3]的计量烷基化反应以88%的区域选择性进行，形成支化产物。
• Calix[4]arene bisphosphite ligands bearing two distal 2,2′-biphenyldioxy or 2,2′-binaphthyldioxy moieties: conformational flexibility and allyl–palladium complexes
  作者：Arindam Sarkar、Setharampattu S. Krishnamurthy、Munirathinam Nethaji

  DOI：10.1016/j.tet.2008.10.031

  日期：2009.1

  1H and 31P NMR evidence strongly supports a similar kind of exchange mechanism for ligand 3. Freezing of the cone conformer from the interconverting C/D pair of conformers of ligand 2 has been achieved by complexation with (allyl)palladium moieties. The methyl–allyl complex (2d) is moderately effective for catalytic regioselective allylic alkylation of crotyl acetate.

  已经合成了分别带有两个远端2，2′-联苯基二氧基次膦氧基和2，2′-联萘二氧基次膦氧基部分的非手性和手性杯[4]芳烃双亚磷酸酯配体（2和3）。这些配体中的每一个都以两对相互转化的构象存在于溶液中。（双）联苯二氧基次膦酸酯氧基配体2的部分圆锥构象体（A）已经通过分步结晶分离，并且其结构通过X射线晶体学确定。已经通过二维NMR光谱法探究了成对的构象体（A / B和C / D）的互变机理。的1 H和31 P NMR证据强烈支持类似种交换机构，用于配体3。通过与（烯丙基）钯部分的络合已经实现了从配体2的相互转化的C / D构象异构体对的锥体构象异构体的冷冻。甲基-烯丙基复合物（2d）对于乙酸巴豆基酯的区域选择性催化烯丙基烷基化反应具有中等效果。
• Catalyst selection based on intermediate stability measured by mass spectrometry
  作者：Jeroen Wassenaar、Eveline Jansen、Willem-Jan van Zeist、F. Matthias Bickelhaupt、Maxime A. Siegler、Anthony L. Spek、Joost N. H. Reek

  DOI：10.1038/nchem.614

  日期：2010.5

  The power of natural selection through survival of the fittest is nature's ultimate tool for the improvement and advancement of species. To apply this concept in catalyst development is attractive and may lead to more rapid discoveries of new catalysts for the synthesis of relevant targets, such as pharmaceuticals. Recent advances in ligand synthesis using combinatorial methods have allowed the generation of a great diversity of catalysts. However, selection methods are few in number. We introduce a new selection method that focuses on the stability of catalytic intermediates measured by mass spectrometry. The stability of the intermediate relates inversely to the reactivity of the catalyst, which forms the basis of a catalyst-screening protocol in which less-abundant species represent the most-active catalysts, ‘the survival of the weakest’. We demonstrate this concept in the palladium-catalysed allylic alkylation reaction using diphosphine and IndolPhos ligands and support our results with high-level density functional theory calculations. Identifying the best catalyst for a particular reaction traditionally involves testing a wide variety of metal and ligand combinations in standard reactions. Here, the best catalyst is found by using mass spectrometry to identify the least stable — and thus most reactive — intermediate in a dynamic mixture of complexes.

  物竞天择、适者生存是大自然改良和提升物种的终极工具。将这一概念应用于催化剂开发具有很大的吸引力，可能会更快地发现用于合成药物等相关目标的新催化剂。近年来，利用组合方法进行配体合成的进展使得催化剂的多样性得以产生。然而，筛选方法却为数不多。我们介绍了一种新的筛选方法，该方法侧重于通过质谱测量催化中间体的稳定性。中间体的稳定性与催化剂的反应活性成反比，这构成了催化剂筛选方案的基础，其中含量较少的物种代表活性最强的催化剂，即 "弱者生存"。我们在使用二膦和吲哚磷配体催化的钯烯丙基烷基化反应中证明了这一概念，并用高水平密度泛函理论计算支持我们的结果。传统上，确定特定反应的最佳催化剂需要在标准反应中测试各种金属和配体组合。在这里，最佳催化剂是通过使用质谱法确定动态混合物中最不稳定的中间体，从而确定反应性最强的中间体。