Dimethyl methyl(1-phenylprop-2-en-1-yl)malonate | 87802-79-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Dimethyl methyl(1-phenylprop-2-en-1-yl)malonate
• 英文别名: Dimethyl methyl(1-phenylprop-2-en-1-yl)propanedioate；dimethyl 2-methyl-2-(1-phenylprop-2-enyl)propanedioate
• CAS: 87802-79-7
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: JJJHTFYISJOMIY-UHFFFAOYSA-N

物化性质

• 沸点：
  309.6±37.0 °C(Predicted)
• 密度：
  1.089±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  甲基丙二酸二甲酯 、 [(COD)Ir(cinnamyl)P(OPh)2(OC6H4)]BF4 在 sodium hydride 作用下， 以 氘代四氢呋喃 为溶剂， 生成 Dimethyl methyl(1-phenylprop-2-en-1-yl)malonate
  参考文献：
  名称：

  Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution

  摘要：

  Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)(3) was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl](2) and P(OPh)(3) by cydometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.

  DOI：

  10.1021/jacs.5b08911

文献信息

• Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of a MOP Ligand
  作者：Tamio Hayashi、Motoi Kawatsura、Yasuhiro Uozumi

  DOI：10.1021/ja973150r

  日期：1998.3.1

  In the palladium-catalyzed allylic alkylation of (E)-3-substituted-2-propenyl acetates (1), 1-substituted-2-propenyl acetates (2), and 1- or 3-deuterio-2-cyclohexenyl acetate (5), which proceeds through 1,3-unsymmetrically substituted π-allylpalladium intermediates, selective substitution at the position originally substituted with acetate was observed by use of a sterically bulky monodentate phosphine

  在钯催化的（E）-3-取代-2-丙烯基乙酸酯（1）、1-取代-2-丙烯基乙酸酯（2）和1-或3-氘代-2-环己烯基乙酸酯（5 )，通过 1,3-不对称取代的 π-烯丙基钯中间体进行，通过使用空间庞大的单齿膦配体 2-(二苯基膦基)-2'-甲氧基-1，观察到最初被乙酸酯取代的位置的选择性取代， 1'-联萘 (MeO-MOP)。通过将 [PdCl(π-环己烯基)]2 与 1 或 2 当量的 MeO-MOP (L*) 混合生成的 π-烯丙基钯配合物的结构研究表明，阳离子双膦配合物 [Pd(L*)2(π-环己烯基) )]+Cl-即使在存在过量配体的情况下也不会形成，但会形成中性单膦配合物 PdCl(L*)(π-环己烯基) (11)，使过量配体游离，并且 11 中 Cl 和 L* 的配位位点的交换比三苯基膦配合物 PdCl(PPh3)(π-环己烯基) (13) 中的交换要慢得多。缓慢的交流可以理性.
• Ruthenium-catalysed linear-selective allylic alkylation of allyl acetates
  作者：Motoi Kawatsura、Fumio Ata、Shohei Wada、Shuichi Hayase、Hidemitsu Uno、Toshiyuki Itoh

  DOI：10.1039/b614015g

  日期：——

  The regioselectivity in the ruthenium-catalysed allylic alkylation of mono substituted allyl acetates with the malonate anion was highly controlled by Ru3(CO)12 with 2-(diphenylphosphino)benzoic acid, and the linear-type alkylated product was obtained.

  通过Ru 3（CO）12与2-（二苯基膦基）苯甲酸的Ru3（CO）12高度控制钌被丙二酸根阴离子单取代的乙酸烯丙酯的烯丙基烷基化反应中的区域选择性，从而获得线性烷基化产物。
• Regiocontrol in palladium-catalysed allylic alkylation by addition of lithium iodide
  作者：Motoi Kawatsura、Yasuhiro Uozumi、Tamio Hayashi

  DOI：10.1039/a707652e

  日期：——

  Regioselectivity in the palladium-catalysed allylic alkylation of 1-arylprop-2-enyl acetates [ArCH(OAc)CHCH2] or (E)-3-phenylprop-2-enyl acetate (PhCHCHCH2OAc) with sodium enolates of soft carbon nucleophiles is controlled by addition of a catalytic amount of lithium iodide to give lienar products [(E)-ArCHCHCH2Nu] exclusively; their branch isomers [ArCH(Nu)CHCH2] were not detected.

  在钯催化的1-芳基丙-2-烯基乙酸酯[ArCH(OAc)CHCH2]或(E)-3-苯丙-2-烯基乙酸酯(PhCHCHCH2OAc)与软碳亲核试剂的钠烯醇盐的亲核烷基化反应中，通过添加催化量的碘化锂可以控制区域选择性，从而独立合成直链产物[(E)-ArCHCHCH2Nu]；其支链异构体[ArCH(Nu)CHCH2]未被检测到。
• Retention of regiochemistry of monosubstituted allyl acetates in the ruthenium catalysed allylic alkylation with malonate anion
  作者：Motoi Kawatsura、Fumio Ata、Shuichi Hayase、Toshiyuki Itoh

  DOI：10.1039/b709218k

  日期：——

  In the RuCl2(p-cymene)/PPh3 catalysed regioselective allylic alkylation of monosubstituted allyl acetates with malonate anion, the selective substitution at the position originally substituted with acetate was observed.

  在RuCl2（对异丙基）/ PPh3催化的单取代的乙酸烯丙酯与丙二酸根阴离子的区域选择性烯丙基烷基化反应中，观察到在最初被乙酸酯取代的位置上的选择性取代。
• Molybdenum(0) and tungsten(0) catalysts with enhanced reactivity for allylic substitution: regioselectivity and solvent effects †
  作者：Andrei V. Malkov、Ian R. Baxendale、Darren J. Mansfield、Pavel Kočovský

  DOI：10.1039/b100903f

  日期：——

  have been developed as pre-catalysts for allylic substitution with β-dicarbonyl nucleophiles. These complexes are reduced in situ to Mo(0) and W(0) catalytic species 30a,b and 31a,b by excess of NaH, employed to generate sodiomalonate nucleophiles, or by DIBAL-H. 1,3-Dioxolane and 1,4-dioxane, when used as solvents, substantially accelerate the reaction. These new catalysts exhibit “traditional” Mo regiochemistry

  已开发出双核Mo（II）和W（II）配合物28a，b和29a，b作为用β-二羰基亲核试剂进行烯丙基取代的预催化剂。这些络合物通过过量的NaH原位还原为Mo（0）和W（0）催化物种30a，b和31a，b，或用于DIBAL-H，该NaH用于生成磺基丙二酸酯亲核试剂。当用作溶剂时，1，3-二氧戊环和1，4-二氧六环大大促进了反应。这些新的催化剂表现出“传统的”区域化学，即，亲核攻击优先发生在取代度更高的碳上（5  →  9 ; 37  →  38），除非像香叶烷基那样，另外一个因素（例如与烯丙基亲电试剂的另一个部分进一步配位）会参与（41）型基板（32或33  →  36）。