diethyl 2-(1-(tert-butoxycarbonyl)-2-oxoindolin-3-ylidene)malonate | 1269701-15-6

• 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: diethyl 2-(1-(tert-butoxycarbonyl)-2-oxoindolin-3-ylidene)malonate
• 英文别名: Diethyl 2-[1-[(2-methylpropan-2-yl)oxycarbonyl]-2-oxoindol-3-ylidene]propanedioate；diethyl 2-[1-[(2-methylpropan-2-yl)oxycarbonyl]-2-oxoindol-3-ylidene]propanedioate
• CAS: 1269701-15-6
• 化学式: C₂₀H₂₃NO₇
• 分子量: 389.405
• InChiKey: NYSOGRVZEMTJLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  99.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  diethyl 2-(1-(tert-butoxycarbonyl)-2-oxoindolin-3-ylidene)malonate 在 sodium tetrahydroborate 、 (2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷 、 水 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 10.5h， 生成 diethyl 6-hydroxy-3-(hydroxymethyl)-2'-oxospiro[cyclohexane-1,3'-indoline]-2,2-dicarboxylate
  参考文献：
  名称：

  Enantioselective construction of multifunctionalized spirocyclohexaneoxindoles through organocatalytic Michael–Aldol cyclization of isatin derived alkenes with linear dialdehydes

  摘要：

  光学活性螺环己氧吲哚基序是制备生物活性复合物、天然产物和药物化合物的非常重要的构建模块。在此，我们报道了在二苯基脯氨醇甲硅烷基醚作为氨基催化剂存在下，通过靛红衍生的烯烃和1,5-二元戊烷之间的多米诺迈克尔·羟醛反应合成对映体纯螺环己烷吲哚。结果，我们以良好的产率获得了一系列具有中等非对映选择性和优异对映选择性的多立体和官能化螺环己氧吲哚。此外，电子圆二色性（ECD）光谱和时间相关密度泛函理论（TD-DFT）被用来研究螺环己氧吲哚的合理结构。

  DOI：

  10.1039/c2ob26205c
• 作为产物：
  描述：

  靛红 在 哌啶 、 4-二甲氨基吡啶 作用下， 以 乙二醇乙醚 、 乙醇 为溶剂， 反应 1.0h， 生成 diethyl 2-(1-(tert-butoxycarbonyl)-2-oxoindolin-3-ylidene)malonate
  参考文献：
  名称：

  Phosphine- and Nitrogen-Containing Lewis Base Catalyzed Highly Regioselective and Geometric Selective Cyclization of Isatin Derived Electron-Deficient Alkenes with Ethyl 2,3-Butadienoate

  摘要：

  An interesting phosphine-containing Lewis base catalyzed highly regioselective [3 + 2] cycloaddition and a novel nitrogen-containing Lewis base catalyzed highly geometric selective [4 + 2] cycloaddition of isatin derived alpha,beta-unsaturated diesters with alpha-allenic ester have been disclosed to give the corresponding cyclic products in good to excellent yields under mild conditions. A plausible reaction mechanism has also been proposed on the basis of previous literature and our own investigation.

  DOI：

  10.1021/ol1031798

文献信息

• Facile Synthesis of Spirooxindole-Cyclohexenes via Phosphine-Catalyzed [4 + 2] Annulation of <i>α</i> -Substituted Allenoates
  作者：Rongshun Chen、Xia Fan、Zhaozhong Xu、Zhengjie He

  DOI：10.1002/cjoc.201700112

  日期：2017.9

  phosphine‐catalyzed [4 + 2] annulation of α‐substituted allenoate with exocyclic alkene moiety of oxindoles or indan‐1,3‐diones has been developed. Thus, under the catalysis of PPh3 (20 mol%), a series of spirooxindole‐ or spiroindan‐1,3‐dione‐cyclohexenes have been obtained in moderate to excellent yields and regioselectivity from the annulations of α‐methyl allenoates with 3‐methyleneoxindoles or 2‐methyleneindan‐1

  已经开发出了膦催化的[4 + 2] α-取代的烯酸酯与羟吲哚或茚满-1,3-二酮的环外烯烃部分的环化反应。因此，在PPh 3（20 mol％）的催化下，从α-甲基烯丙基酸酯与3-甲基环戊酸酯的环化反应中获得了中等至极好的产率和区域选择性的一系列螺环吲哚或spiroindan-1,3-二酮-环己烯。亚甲基吲哚或2-亚甲基茚满-1,3-二酮。这种方法提供了结构上新颖的螺环己烯的简便途径。
• Asymmetric Synthesis of Spiro-3,3′-cyclopropyl Oxindoles via Vinylogous Michael Initiated Ring Closure Reaction
  作者：Abhijit Manna、Harshit Joshi、Vinod K. Singh

  DOI：10.1021/acs.joc.2c02402

  日期：2022.12.16

  A novel organocatalytic cascade approach for the synthesis of spiro-cyclopropyl oxindole derivatives has been developed. The methodology is based on asymmetric vinylogous Michael addition of 4-nitroisoxazole derivatives to N-Boc isatylidene malonates followed by intramolecular alkylation. Its remarkable stereocontrol, wide substrate scope, and scalability highlight this new developed strategy. Moreover

  开发了一种用于合成螺-环丙基羟吲哚衍生物的新型有机催化级联方法。该方法基于 4-硝基异恶唑衍生物与N -Boc 异亚甲基丙二酸酯的不对称插烯迈克尔加成反应，然后进行分子内烷基化。其卓越的立体控制、广泛的基板范围和可扩展性突出了这一新开发的策略。此外，这项工作代表了用于合成手性 3,3'-环丙基羟吲哚的插烯迈克尔引发闭环 (MIRC) 反应的第一个例子。
• Access to Spirooxindole-Fused Cyclopentanes via a Stereoselective Organocascade Reaction Using Bifunctional Catalysis
  作者：Andrea Vopálenská、Vojtěch Dočekal、Simona Petrželová、Ivana Císařová、Jan Veselý

  DOI：10.1021/acs.joc.2c02478

  日期：——

  The present study reports an asymmetric organocascade reaction of oxindole-derived alkenes with 3-bromo-1-nitropropane efficiently catalyzed by the bifunctional catalyst. Spirooxindole-fused cyclopentanes were produced in moderate-to-good isolated yields (15–69%) with excellent stereochemical outcomes. The synthetic utility of the protocol was exemplified on a set of additional transformations of the

  本研究报告了由双功能催化剂有效催化的羟吲哚衍生烯烃与3-溴-1-硝基丙烷的不对称有机级联反应。螺吲哚稠合环戊烷的分离产率中等至良好（15-69%），具有优异的立体化学结果。该方案的合成效用通过相应螺吲哚化合物的一组附加转化进行了例证。
• Phosphine- and Nitrogen-Containing Lewis Base Catalyzed Highly Regioselective and Geometric Selective Cyclization of Isatin Derived Electron-Deficient Alkenes with Ethyl 2,3-Butadienoate
  作者：Xiu-Chun Zhang、Shu-Hua Cao、Yin Wei、Min Shi

  DOI：10.1021/ol1031798

  日期：2011.3.4

  An interesting phosphine-containing Lewis base catalyzed highly regioselective [3 + 2] cycloaddition and a novel nitrogen-containing Lewis base catalyzed highly geometric selective [4 + 2] cycloaddition of isatin derived alpha,beta-unsaturated diesters with alpha-allenic ester have been disclosed to give the corresponding cyclic products in good to excellent yields under mild conditions. A plausible reaction mechanism has also been proposed on the basis of previous literature and our own investigation.
• Enantioselective construction of multifunctionalized spirocyclohexaneoxindoles through organocatalytic Michael–Aldol cyclization of isatin derived alkenes with linear dialdehydes
  作者：Xiao-Fei Huang、Zhao-Min Liu、Zhi-Cong Geng、Shao-Yun Zhang、Yong Wang、Xing-Wang Wang

  DOI：10.1039/c2ob26205c

  日期：——

  Optically active spirocyclohexaneoxindole motifs are very important building blocks for preparations of biologically active complexes, natural products, and pharmaceutical compounds. Herein, we report the syntheses of enantiopure spirocyclohexaneoxindoles through domino Michael–Aldol reactions between isatin derived alkenes and pentane-1,5-dial in the presence of diphenylprolinol silyl ether as an aminocatalyst. As a result, a series of multistereogenic and functionalized spirocyclohexaneoxindoles have been obtained in good yields with moderate diastereoselectivities and excellent enantioselectivities. In addition, electronic circular dichroism (ECD) spectroscopy and time-dependent density functional theory (TD-DFT) were used to investigate the rational structures of spirocyclohexaneoxindoles.

  光学活性螺环己氧吲哚基序是制备生物活性复合物、天然产物和药物化合物的非常重要的构建模块。在此，我们报道了在二苯基脯氨醇甲硅烷基醚作为氨基催化剂存在下，通过靛红衍生的烯烃和1,5-二元戊烷之间的多米诺迈克尔·羟醛反应合成对映体纯螺环己烷吲哚。结果，我们以良好的产率获得了一系列具有中等非对映选择性和优异对映选择性的多立体和官能化螺环己氧吲哚。此外，电子圆二色性（ECD）光谱和时间相关密度泛函理论（TD-DFT）被用来研究螺环己氧吲哚的合理结构。