sodium dimethyl methylmalonate | 62116-54-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: sodium dimethyl methylmalonate
• CAS: 62116-54-5
• 化学式: C₆H₉NaO₄
• 分子量: 168.125
• InChiKey: VICAOCYCWDTXTK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  36.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  sodium dimethyl methylmalonate 、 2-cyclopropylidene-1-phenoxy propane 在 palladium diacetate 、 三苯基膦 作用下， 生成 dimethyl-(2-cyclopropylidenepropyl)-methyl malonate
  参考文献：
  名称：

  Palladium (0) Catalyzed Nucleophilic Substitution On 2-Cyclopropylidene-phenoxy Ethanes

  摘要：

  2-cyclopropylidene-phenoxy ethanes 5, 2-substituted with alkyl, aryl or heterocyclic groups are readily obtained in high yields by the Wittig reaction of the easily accessible a-phenoxy etanones 4 with (3-bromo propyl) triphenylphosphonium bromide. They react with complete regioselectivity in palladium (0) catalyzed nucleophilic substitutions with a series of soft carbon nucleophiles giving an easy entry to 5,6-methanoamino acids.

  DOI：

  10.1080/00397919708004192
• 作为试剂：
  描述：

  2-Methyl-2-(3-methyl-1-vinyl-but-2-enyl)-malonic acid dimethyl ester 在 palladium diacetate 、 三丁基膦 、 sodium dimethyl methylmalonate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 2-Methyl-2-((E)-5-methyl-hexa-2,4-dienyl)-malonic acid dimethyl ester
  参考文献：
  名称：

  Nilsson, Ylva I.M.; Andersson, Pher G.; Bäckvall, Jan-E., Journal of the American Chemical Society, 1993, vol. 115, # 15, p. 6609 - 6613

  摘要：

  DOI：

文献信息

• 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。
• Palladium Assisted Alkylation-Insertion Reactions of Chiral Ene-Carbamates
  作者：Guy J. Laidig、Louis S. Hegedus

  DOI：10.1055/s-1995-3960

  日期：1995.5

  Palladium(II) complexes of chiral ene-carbamate 2 underwent efficient, stereoselective alkylation by malonate carbanions having pendent unsaturated side chains. The resulting σ-alkylpalladium(II) complexes underwent efficient insertion of carbon monoxide to produce esters. Insertion of the pendent unsaturated groups was less efficient, and led to mixtures of insertion products with little stereoselectivity.

  手性烯丙基氨基酸盐 2 的钯(II) 配合物通过具有悬挂不饱和侧链的马来酸盐碳负离子高效地进行了立体选择性烷基化。所得的 σ-烷基钯(II) 配合物经历了高效的二氧化碳插入反应，生成酯。悬挂不饱和基团的插入效率较低，导致插入产物的混合，并且立体选择性较差。
• Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl)silanes and Chirality Transfer to Stereogenic Carbon Centers in S_E‘ Reactions
  作者：Masamichi Ogasawara、Kazuhito Ueyama、Takashi Nagano、Yoshiyuki Mizuhata、Tamio Hayashi

  DOI：10.1021/ol027291w

  日期：2003.1.1

  [reaction: see text] Novel stereoselective reactions of 4-substituted-1-trimethylsilyl-2,3-butadienes ((allenylmethyl)silanes) were developed. The axially chiral (allenylmethyl)silanes were prepared from (3-bromopenta-2,4-dienyl)trimethylsilane by a Pd-catalyzed asymmetric reaction with soft nucleophiles with up to 88% enantioselectivity. The (allenylmethyl)silanes reacted with acetals in the presence

  [反应：见正文]开发了4-取代的-1-三甲基甲硅烷基-2,3-丁二烯（（烯丙基甲基）硅烷）的新型立体选择性反应。轴向手性（烯丙基甲基）硅烷是由（3-溴戊-2,4-二烯基）三甲基硅烷通过Pd催化的不对称反应与柔软的亲核试剂以高达88％的对映选择性制备的。（烯丙基甲基）硅烷在TiCl（4）助催化剂的存在下与缩醛反应，通过S（E）'途径生成1,3-二烯衍生物。1,3-二烯基产物仅具有（E）-几何形状，并且在S（E）'反应中观察到高达88％（）（）手性从轴向手性亚烯基转移到中心手性1,3-二烯。
• Vinyl Ketones to Allenes:  Preparation of 1,3-Dien-2-yl Triflates and Their Application in Pd-Catalyzed Reactions with Soft Nucleophiles
  作者：Masamichi Ogasawara、Yonghui Ge、Koichi Uetake、Tamotsu Takahashi

  DOI：10.1021/ol052426u

  日期：2005.12.1

  [chemical reaction: see text]. A general route of converting alkenyl ketones to functionalized allenes was developed. Substituted 1,3-dien-2-yl triflates, which were prepared from the alkenyl ketones via silyl dienol ethers, were excellent substrates for the palladium-catalyzed reaction with soft nucleophiles giving the multisubstituted allenes in high yields. Comparison between the dienyl triflates and

  [化学反应：见正文]。开发了将烯基酮转化为官能化的烯的一般路线。由烯基酮经甲硅烷基二烯醇醚制备的1,3-二烯-2-基三氟甲磺酸酯是钯与软亲核试剂催化反应的极佳底物，可高收率得到多取代的烯。还研究了在Pd催化的反应中二烯基三氟甲磺酸酯和类似溴代亚胺之间的比较。
• New reactions involving palladacyclobutanes: The attack of phenoxide ion at the central carbon of both 1- and 2-bromo(π-allyl)palladium complexes
  作者：Michael G Organ、Michael Miller

  DOI：10.1016/s0040-4039(97)10252-0

  日期：1997.11

  Nucleophilic attack of phenoxide ion occurs primarily at the central carbon of halo-substituted (π-allyl)Pd complexes.

  酚盐离子的亲核攻击主要发生在卤素取代的（π-烯丙基）Pd配合物的中心碳上。