allyl 3-(methyl(phenyl)amino)-3-oxopropanoate | 1319767-67-3

• 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: allyl 3-(methyl(phenyl)amino)-3-oxopropanoate
• 英文别名: prop-2-enyl 3-(N-methylanilino)-3-oxopropanoate
• CAS: 1319767-67-3
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: XFQULGROOUDYFR-UHFFFAOYSA-N

物化性质

• 沸点：
  349.0±25.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  allyl 3-(methyl(phenyl)amino)-3-oxopropanoate 在 potassium tert-butylate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二甲基亚砜 为溶剂， 生成 allyl 3-benzyl-1-methyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  DDQ-mediated Direct Intramolecular-Dehydrogenative-Coupling (IDC): Expeditious Approach to the Tetracyclic Core of Ergot Alkaloids

  摘要：

  An efficient route to 2-oxindoles bearing an all-carbon quaternary center at the pseudobenzylic position has been developed via a DDQ-mediated Intramolecular-Dehydrogenative-Coupling (IDC). The methodology involves a one-pot C-alkylation of beta-N-arylamido esters (7) concomitant with dehydrogenative-coupling in the presence of stoichiometric amount of DDQ. A tentative mechanistic route has been proposed for the oxidative coupling. The methodology provides a two-step entry to the ergoline structure of ergot alkaloids.

  DOI：

  10.1021/ol400899e
• 作为产物：
  描述：

  N-甲基苯胺 在 三乙烯二胺 、 N-碘代丁二酰亚胺 、 水 、 palladium diacetate 、 silver nitrate 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 21.0h， 生成 allyl 3-(methyl(phenyl)amino)-3-oxopropanoate
  参考文献：
  名称：

  Palladium-Catalyzed Alcoholysis of 3-Iodopropynamides: Selective Synthesis of Carbamoylacetates

  摘要：

  A novel and selective method for the synthesis of carbamoylacetates via the alcoholysis of 3-iodopropynamides has been developed. 3-Iodopropynamides react with alcohols in the presence of palladium(II) acetate and DABCO to afford the corresponding carbamoylacetates in moderate to good yields.

  DOI：

  10.1055/s-0034-1379104

文献信息

• Enantioselective synthesis of sterically hindered α-allyl–α-aryl oxindoles via palladium-catalysed decarboxylative asymmetric allylic alkylation
  作者：Mark Jackson、Calvin Quince O'Broin、Helge Müller-Bunz、Patrick J. Guiry

  DOI：10.1039/c7ob02161e

  日期：——

  decarboxylative asymmetric allylic alkylation (DAAA) was optimized with 2,4,6-trimethoxyphenyl as the aryl-containing substrate. A screen of chiral P,N- and P,P-based ligands showed that the ANDEN-phenyl Trost ligand was the most effective, affording the corresponding α-allyl–α-aryl oxindole product in 96% yield and 99% ee. A substrate scope of a further 12 α-aryl–β-amido allyl ester substituted oxindoles showed

  已开发出在对羟基3位具有全碳四级立体中心的位阻α-烯丙基-α-芳基羟基吲哚的高对映选择性合成。合成途径中的关键步骤是新颖的一锅，两步合成α-芳基-β-酰胺基烯丙基酯取代的羟吲哚，通过拦截不稳定的烯丙基酯以41-75％的高收率（13个实例）通过与三乙酸芳基铅试剂反应生成中间体。以2,4,6-三甲氧基苯基作为含芳基的底物优化了钯催化的脱羧不对称烯丙基烷基化反应（DAAA）。手性P，N-和P，P的屏幕基配体表明，ANDEN-苯基Trost配体最有效，以96％的收率和99％ee的产率提供相应的α-烯丙基-α-芳基羟吲哚产物。另有12个α-芳基-β-酰胺基烯丙基酯取代的羟吲哚的底物范围显示，在高ee（94-98％）的情况下会形成含有庞大的二-邻甲氧基取代的芳烃和萘基的产物，而缺少这些的替代模式是在中等水平的对映选择性（56-63％ee）下形成的。出乎意料的是，与预期的C相反，2,6-二甲基苯基取代的
• Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp² C–H and sp³ C–H bonds
  作者：Nivesh Kumar、Santanu Ghosh、Subhajit Bhunia、Alakesh Bisai

  DOI：10.3762/bjoc.12.111

  日期：——

  benzylic position has been achieved via a 'transition-metal-free' intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon-carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of beta-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for

  经由“无过渡金属”的分子内脱氢偶联（IDC），已经完成了在假苄基位置带有全碳季中心的各种2-氧吲哚的合成。通过使用KOt-Bu催化β-N-芳基酰胺酯与烷基卤化物的一锅C-烷基化，然后脱氢偶联，通过形成碳-碳键来进行2-氧吲哚部分的构建。实验证据表明该反应朝向自由基介导的途径。
• Asymmetric Decarboxylative Allylation of Oxindoles
  作者：Vilius Franckevičius、James D. Cuthbertson、Mark Pickworth、David S. Pugh、Richard J. K. Taylor

  DOI：10.1021/ol201613a

  日期：2011.8.19

  An asymmetric decarboxylative palladium-catalyzed allylation of alkyl- and aryl-substituted oxindoles has been developed, enabling the installation of an all-carbon quaternary chiral center at the oxindole 3-position in excellent yields and good to excellent enantioselectivity. An intriguing substrate-dependent reversal in stereoselectivity has been observed, whereby the size of the substituent determines the facial selectivity in the allylation step.
• Intramolecular Dehydrogenative Coupling of sp² C–H and sp³ C–H Bonds: An Expeditious Route to 2-Oxindoles
  作者：Santanu Ghosh、Subhadip De、Badrinath N. Kakde、Subhajit Bhunia、Amit Adhikary、Alakesh Bisai

  DOI：10.1021/ol302767w

  日期：2012.12.7

  An intramolecular-dehydrogenative-coupling (IDC) using "transition-metal-free" oxidation conditions has been achieved to synthesize a variety of 2-oxindoles bearing an all-carbon quaternary stereogenic center at the benzylic position. The methodology involves a one-pot C-alkylation of beta-N-arylamido esters (3, 6) with alkyl halides using potassium tert-butoxide concomitant with a dehydrogenative coupling. A radical-mediated pathway has been tentatively proposed for the oxidative process.