[3-13C]allyl benzoate | 352664-57-4

• 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: [3-13C]allyl benzoate
• 英文别名: (13)C1-allyl benzoate；(313C)prop-2-enyl benzoate
• CAS: 352664-57-4
• 化学式: C₁₀H₁₀O₂
• 分子量: 163.177
• InChiKey: LYJHVEDILOKZCG-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙酸烯丙酯 、 sodium;(E)-1,3-dimethoxy-2-methyl-3-oxoprop-1-en-1-olate 、 [3-13C]allyl benzoate 在 [bis(triphenylphosphine)allylpalladium(II)] triflate 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 C₈⁽¹³⁾CH₁₄O₄ 、 C₈⁽¹³⁾CH₁₄O₄ 、 dimethyl 2-allyl-2-methylmalonate
  参考文献：
  名称：

  Counterintuitive Kinetics in Tsuji-Trost Allylation: Ion-Pair Partitioning and Implications for Asymmetric Catalysis

  摘要：

  The kinetics of Pd-catalyzed Tsuji-Trost allylation employing simple phosphine ligands (L = Ar3P, etc.) are consistent with turnover-limiting nucleopile attack of an electrophilic [L2Pd(allyl)](+) catalytic intermediate. Counter-intuitively, when L is made more electron donating, whcih renders [L2Pd(allyl)](+) less electrophilic (by up to an order of magnitude), higher rates of turnover are observed. In the presence of catalytic NaBArF, large rate differentials arise by attenuation of ion-pair return (via generation of [L2Pd(allyl)](+)//[BAr'F](-))a process that also increases the asymmetric induction from 28 to 78% ee in an archetypal assymmetric allylation employing BINAP (L*) as ligand. There is substantial potential for analogous application of (M)(n+) ([BAr'F](-))(n) cocatalysis in other transition metal catalyzed processes involving an ionic reactant or reagent and an ionogenic catalytic cycle.

  DOI：

  10.1021/ja806278e
• 作为产物：
  描述：

  2-benzoyloxyacetaldehyde 、 甲基-13C-三苯基碘化膦 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以67%的产率得到[3-13C]allyl benzoate
  参考文献：
  名称：

  [2H,13C]-标记的二烯丙丙二酸酯的合成 - 用于研究过渡金属催化的 1,6-二烯环异构化的有用探针

  摘要：

  已开发出同位素标记的二甲基 [13C,2H] 二烯丙基丙二酸酯 (1) 的可靠合成路线。二甲基二烯丙基丙二酸酯很容易经历过渡金属催化的环异构化，并且同位素标记的底物有望在此类反应机理的研究中具有普遍用途。在开发的合成路线中，通过使用 Schwartz 试剂还原炔丙基官能团来引入 2H 标记的烯丙基链。这种反应的区域和立体选择性允许高选择性标记策略。使用 [3-13C1] 苯甲酸烯丙酯作为烯丙基亲电试剂，通过 Pd 催化的 13C 或 2H 标记的二甲基烯丙基丙二酸阴离子的烯丙基烷基化引入 13C 标记的烯丙基链。使用这些方法，二甲基 [1,7-(E,E)-2H2]hept-1,6-dienyl-4,4-dicarboxylate (5), 二甲基 [2,

  DOI：

  10.1002/1099-0690(200105)2001:9<1635::aid-ejoc1635>3.0.co;2-c

文献信息

• Synthesis of [2H,13C]-Labelled Diallylmalonates − Useful Probes for the Study of Transition Metal-Catalysed 1,6-Diene Cycloisomerisation
  作者：Katharine L. Bray、Guy C. Lloyd-Jones

  DOI：10.1002/1099-0690(200105)2001:9<1635::aid-ejoc1635>3.0.co;2-c

  日期：2001.5

  Reliable synthetic routes to isotopically labelled dimethyl [13C,2H]diallylmalonates (1) have been developed. Dimethyl diallylmalonates readily undergo transition-metal catalysed cycloisomerisation and the isotopically labelled substrates are expected to be of general utility in the study of the mechanism of such reactions. In the synthetic routes developed, the 2H labelled allyl chains were introduced

  已开发出同位素标记的二甲基 [13C,2H] 二烯丙基丙二酸酯 (1) 的可靠合成路线。二甲基二烯丙基丙二酸酯很容易经历过渡金属催化的环异构化，并且同位素标记的底物有望在此类反应机理的研究中具有普遍用途。在开发的合成路线中，通过使用 Schwartz 试剂还原炔丙基官能团来引入 2H 标记的烯丙基链。这种反应的区域和立体选择性允许高选择性标记策略。使用 [3-13C1] 苯甲酸烯丙酯作为烯丙基亲电试剂，通过 Pd 催化的 13C 或 2H 标记的二甲基烯丙基丙二酸阴离子的烯丙基烷基化引入 13C 标记的烯丙基链。使用这些方法，二甲基 [1,7-(E,E)-2H2]hept-1,6-dienyl-4,4-dicarboxylate (5), 二甲基 [2,
• Counterintuitive Kinetics in Tsuji-Trost Allylation: Ion-Pair Partitioning and Implications for Asymmetric Catalysis
  作者：Louise A. Evans、Natalie Fey、Jeremy N. Harvey、David Hose、Guy C. Lloyd-Jones、Paul Murray、A. Guy Orpen、Robert Osborne、Gareth J. J. Owen-Smith、Mark Purdie

  DOI：10.1021/ja806278e

  日期：2008.11.5

  The kinetics of Pd-catalyzed Tsuji-Trost allylation employing simple phosphine ligands (L = Ar3P, etc.) are consistent with turnover-limiting nucleopile attack of an electrophilic [L2Pd(allyl)](+) catalytic intermediate. Counter-intuitively, when L is made more electron donating, whcih renders [L2Pd(allyl)](+) less electrophilic (by up to an order of magnitude), higher rates of turnover are observed. In the presence of catalytic NaBArF, large rate differentials arise by attenuation of ion-pair return (via generation of [L2Pd(allyl)](+)//[BAr'F](-))a process that also increases the asymmetric induction from 28 to 78% ee in an archetypal assymmetric allylation employing BINAP (L*) as ligand. There is substantial potential for analogous application of (M)(n+) ([BAr'F](-))(n) cocatalysis in other transition metal catalyzed processes involving an ionic reactant or reagent and an ionogenic catalytic cycle.