Methyl 3-bromo-2-(1-methyl-2-oxoindol-3-ylidene)propanoate | 1156547-66-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: Methyl 3-bromo-2-(1-methyl-2-oxoindol-3-ylidene)propanoate
• CAS: 1156547-66-8
• 化学式: C₁₃H₁₂BrNO₃
• 分子量: 310.147
• InChiKey: ZXZUBRGHGYQWRX-UHFFFAOYSA-N

物化性质

• 沸点：
  396.6±42.0 °C(Predicted)
• 密度：
  1.541±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• 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：

  Methyl 3-bromo-2-(1-methyl-2-oxoindol-3-ylidene)propanoate 在 potassium carbonate 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以51%的产率得到methyl 2-(1-methyl-2-oxoindolin-3-ylidene)propanoate
  参考文献：
  名称：

  通过1,3-偶极环加成反应有效地立体合成3-spirocyclopentene-和3-spiropyrazole-2-oxindoles。

  摘要：

  磷和硫的化学信息已被用于由Isita的Morita-Baylis-Hillman加成物的溴衍生物的E-和Z-异构体轻松快速，短而有效地合成3-spirocyclopentene-和3-spiropyrazole-2-oxindoles Ph（3）P /活化的烯烃/ K（2）CO（3）和Me（2）S / DEAD / K（2）CO（3），分别通过[3 + 2]-环化策略。

  DOI：

  10.1039/b924066g
• 作为产物：
  描述：

  methyl 2-(3-hydroxy-1-methyl-2-oxoindolin-3-yl)acrylate 在 氢溴酸 、 potassium carbonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 4.0h， 生成 Methyl 3-bromo-2-(1-methyl-2-oxoindol-3-ylidene)propanoate
  参考文献：
  名称：

  Unprecedented One-Pot, Domino Tertiary Alcohol Protection–Michael Type Addition of Halides to Morita–Baylis–Hillman Adduct of Isatin with RCOX/K₂CO₃: Diastereoselective Synthesis of Oxindole Appended β-Halo Esters

  摘要：

  A facile method utilizing RDOX/K2CO3 as a novel reagent for conjugate addition of hydrogen halide, in addition to tertiary (3 degrees)-hydroxyl protection that leads to the synthesis of functionalized beta-halo Morita-Baylis-Hillman ester appended oxindoles, has been developed. The diastereoselective one-pot O-acylation-hydrohalogenation observed cannot otherwise be performed by treatment with hydrohalide. Deprotection of a 3 degrees-hydroxyl protecting group has also been demonstrated by treatment with hydrochloric acid.

  DOI：

  10.1021/ol303554c

文献信息

• Pyridine Core Activation <i>via</i> 1,5-Electrocyclization of Vinyl Pyridinium Ylides Generated from Bromo Isomerized Morita−Baylis−Hillman Adduct of Isatin and Pyridine: Synthesis of 3-Spirodihydroindolizine Oxindoles
  作者：Baby Viswambharan、Kodirajan Selvakumar、Suchithra Madhavan、Ponnusamy Shanmugam

  DOI：10.1021/ol100591r

  日期：2010.5.7

  5-electrocyclization of vinyl pyridinium ylides generated from bromo isomerized Morita−Baylis−Hillman adducts of isatin and pyridine under basic conditions. The method has been successfully applied for an efficient synthesis of a number of 3-spirodihydroindolizine-2-oxindoles, which have been found as core structure of secoyohimbane and heteroyohimbane alkaloid natural products.

  吡啶核的活化是通过在碱性条件下，由溴化异构化的Morita-Baylis-Hillman加合物的Isatin和吡啶生成的乙烯基吡啶鎓的乙烯基吡啶进行的1,5-电环化实现的。该方法已成功地用于许多3-螺二氢吲哚嗪-2-氧吲哚的高效合成，这些3-螺二氢吲哚嗪-2-氧吲哚已被发现为七代育亨宾和杂代育亨生物碱天然产物的核心结构。
• [4 + 3] Cycloadditions with Bromo-Substituted Morita–Baylis–Hillman Adducts of Isatins and<i>N</i>-(<i>ortho</i>-Chloromethyl)aryl Amides
  作者：Gu Zhan、Ming-Lin Shi、Qing He、Wei Du、Ying-Chun Chen

  DOI：10.1021/acs.orglett.5b02279

  日期：2015.10.2

  Efficient construction of a challenging aza-spirocycloheptane oxindole scaffold is reported through an unprecedented [4 + 3] cycloaddition reaction with bromo-substituted Morita–Baylis–Hillman adducts of isatins and N-(ortho-chloromethyl)aryl amides. Both reactive intermediates, the allylic phosphonium ylides and aza-o-quinone methides, were in situ generated, chemoselectively facilitated by a Lewis

  通过空前的[4 + 3]环取代反应，与靛红和N-（邻-氯甲基）芳基酰胺的溴取代的Morita-Baylis-Hillman加合物进行了空前的[4 + 3]环加成反应，报道了一种具有挑战性的aza-spirocycloheptane oxindole支架的有效构建。两种反应性中间体，即烯丙基磷鎓叶立德和氮杂-邻醌甲基化物，均是在原位生成的，分别通过路易斯碱和布朗斯台德碱进行了化学选择性的促进。
• Stereoselective Synthesis of Geometrically Strained, Oxindole-Appended Vinyl Cyclopropanes and Highly Substituted Cyclopentenes via Sulfur Ylide Cyclopropanation and Vinyl Cyclopropane Rearrangement
  作者：Ponnusamy Shanmugam、Kandapalam Lingam、Kodirajan Selvakumar

  DOI：10.1055/s-0031-1290077

  日期：2012.1

  An efficient diastereoselective synthesis of oxindole-­appended vinyl cyclopropanes from bromo isomerised Morita-Baylis-Hillman adducts of isatin with activated alkylidene and isatilidines via sulfur ylide cyclopropanation reaction have been achieved. The synthesised vinyl cyclopropanes have undergone vinyl cyclopropane rearrangement and [3+2] cycloaddition with an allene to afford dispiro bisoxindole

  通过溴化硫代内酯环丙烷化反应，由活化的亚烷基和异戊二烯经溴化异构化的Isita的Morita-Baylis-Hillman加合物，实现了对非吲哚选择性的乙烯基环丙烷的非对映选择性合成。合成的乙烯基环丙烷已经经历了乙烯基环丙烷重排和与丙二烯的[3 + 2]环加成反应，分别制得了由环戊烯和螺环戊烯-2-氧吲哚桥连的螺环环丙烷-2-氧吲哚衍生物桥接的双螺双氧并吲哚。 非对映选择性合成-乙烯基环丙烷-乙烯基环丙烷重排-[3 + 2]环加成
• A Short and Efficient Synthesis of 3-Spiro-α-methylene-γ-butyrolactone Oxindolones from Isomerised Bromo Derivatives of Morita-Baylis-Hillman Adducts
  作者：Ponnusamy Shanmugam、Baby Viswambharan

  DOI：10.1055/s-0028-1083549

  日期：——

  A short and efficient synthesis of α-methylene-γ-butyrolactone-3-spirooxindolones by the reaction of isomerised bromo derivatives of Morita-Baylis-Hillman adducts of isatin and formaldehyde followed by acid-catalysed lactonisation has been achieved. The oxindolidino allyl bromide has been used for the first time for the allylation of aldehydes to afford a 2-oxindolidino homoallylic alcohol which on

  通过靛红和甲醛的 Morita-Baylis-Hillman 加合物的异构化溴衍生物反应，然后进行酸催化内酯化反应，快速有效地合成了 α-亚甲基-γ-丁内酯-3-spioxoxindolones。oxindolidino 烯丙基溴首次用于醛的烯丙基化，以提供 2-oxindolidino 高烯丙醇，该醇在酸催化内酯化时以优异的产率提供标题化合物。通过环氧乙烷衍生物和第二个 Morita-Baylis-Hillman 加合物的制备证明了螺内酯 oxindole 的合成转化。
• A novel MgI2 mediated unusual dimerization–spirocyclopropanation of bromo isomerised Morita–Baylis–Hillman adduct of isatin: a facile synthesis of 3-spirocyclopropane-2-oxindole derivatives
  作者：Kandapalam Arun Prasath Lingam、Asit Baran Mandal、Ponnusamy Shanmugam

  DOI：10.1016/j.tetlet.2011.05.009

  日期：2011.7

  A novel magnesium iodide mediated unusual dimerization–spirocyclopropanation of bromo isomerised Morita–Baylis–Hillman adducts of isatin afforded highly functionalized 3-spirocyclopropane-2-oxindole derivatives as regioisomers in good combined yield. It has been observed that the regioselectivity is dependent on the nature of electron withdrawing group at the activated position. A plausible mechanism

  新型的碘化镁介导的溴异构化的森田-贝利斯-希尔曼加成反应不寻常的二聚化-螺环丙烷化，得到了功能强大的3-螺环丙烷-2-氧吲哚衍生物，具有很高的区域收率。已经观察到区域选择性取决于活化位置上的吸电子基团的性质。已经提出了一种涉及有机镁试剂的合理机理。