dimethyl 1,1'-dimethyl-2,2'-dioxo-[3,3'-biindoline]-3,3'-dicarboxylate | 1410941-30-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 1,1'-dimethyl-2,2'-dioxo-[3,3'-biindoline]-3,3'-dicarboxylate
• 英文别名: dimethyl-1,1′-dimethyl-2,2′-dioxo-[3,3′-biindoline]-3,3′-dicarboxylate；methyl (3S)-3-[(3R)-3-methoxycarbonyl-1-methyl-2-oxoindol-3-yl]-1-methyl-2-oxoindole-3-carboxylate
• CAS: 1410941-30-8
• 化学式: C₂₂H₂₀N₂O₆
• 分子量: 408.411
• InChiKey: SCKCZVXHMAMKON-SZPZYZBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  93.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  N-甲基吲哚酮 在 potassium tert-butylate 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 、 mineral oil 为溶剂， 反应 1.33h， 生成 dimethyl 1,1'-dimethyl-2,2'-dioxo-[3,3'-biindoline]-3,3'-dicarboxylate 、 dimethyl 1,1'-dimethyl-2,2'-dioxo-[3,3'-biindoline]-3,3'-dicarboxylate
  参考文献：
  名称：

  Oxidative Dimerization of 2-Oxindoles Promoted by KO^tBu-I₂: Total Synthesis of (±)-Folicanthine

  摘要：

  A transition-metal-free oxidative coupling of 2-oxindoles has been demonstrated in the presence of 1.2 equiv each of potassium tert-butoxide and iodine. The method yields a diverse range of structurally different homo- and heterodimerized 2-oxindoles bearing vicinal all-carbon quaternary centers of great synthetic importance. A radical-driven pathway has been tentatively proposed.

  DOI：

  10.1021/acs.orglett.5b00032

文献信息

• 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。
• Electrochemical Synthesis of Dimeric 2-Oxindole Sharing Vicinal Quaternary Centers Employing Proton-Coupled Electron Transfer
  作者：Sulekha Sharma、Avishek Roy、Kundan Shaw、Alakesh Bisai、Amit Paul

  DOI：10.1021/acs.joc.0c01621

  日期：2020.12.4

  building blocks for the total synthesis of pyrroloindoline alkaloids. Furthermore, this work demonstrates in-depth mechanistic insights employing electrochemistry, which suggests a stepwise one proton transfer (PT) and two electron transfer (ET) processes. Most significantly, reaction rate acceleration has been demonstrated by exploiting the base-assisted proton-coupled electron transfer (PCET) pathway. Hence

  已经在温和的电化学条件下开发了3-取代的2-氧吲哚的二聚反应，避免了有毒的化学氧化剂和金属副产物。这种方法形成了C（sp 3）–C（sp 3）在具有广泛的底物范围的2-氧吲哚的两个配偶体的假苄基位置键合。这些二聚体结构基序是吡咯并吲哚啉生物碱总合成的重要组成部分。此外，这项工作展示了利用电化学的深入机械学见解，这表明了逐步的一个质子转移（PT）和两个电子转移（ET）过程。最重要的是，通过利用碱辅助的质子耦合电子转移（PCET）途径已证明了反应速率的加快。因此，这项工作借助自然界最喜欢的动力学途径（即PCET），在有机合成领域开辟了新的领域，以降低动力学障碍。
• Enantioselective Oxidative Enolate Coupling of Oxindoles Catalyzed by Chiral Guanidinium Hypoiodite
  作者：Minami Odagi、Io Mori、Kota Sugimoto、Kazuo Nagasawa

  DOI：10.1021/acscatal.2c05677

  日期：2023.2.17

  Hypoiodite is an environmentally friendly oxidant that has been developed to drive a variety of bond-forming reactions. Recently, asymmetric oxidative bond-forming reactions using hypoiodite in the presence of chiral onium organocatalysts have been used to synthesize carbon–heteroatom bonds, but asymmetric carbon–carbon bond-forming reactions have not been reported. Herein, we present an oxidative

  次碘酸盐是一种环境友好型氧化剂，已开发用于驱动各种成键反应。最近，在手性有机催化剂存在下使用次碘酸盐的不对称氧化键形成反应已被用于合成碳 - 杂原子键，但尚未报道不对称碳 - 碳键形成反应。在此，我们提出了羟吲哚的氧化烯醇化物偶联反应，使用手性次碘酸胍催化剂提供具有连续全碳季立体异构中心的光学活性羟吲哚二聚体。该反应提供了具有高对映选择性的相应自偶联产物。我们还描述了两个带有不同电子取代基的羟吲哚的氧化烯醇化物交叉偶联反应。
• 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.