methyl 2-(3-hydroxy-1-methyl-2-oxoindolin-3-yl)acrylate

• 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 2-(3-hydroxy-1-methyl-2-oxoindolin-3-yl)acrylate
• 英文别名: Methyl 2-(3-hydroxy-1-methyl-2-oxoindolin-3-yl)acrylate；methyl 2-(3-hydroxy-1-methyl-2-oxoindol-3-yl)prop-2-enoate
• 化学式: C₁₃H₁₃NO₄
• 分子量: 247.251
• InChiKey: SZAVAWPCUWGYBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 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：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  methyl 2-(3-((tert-butoxycarbonyl)oxy)-1-methyl-2-oxoindolin-3-yl)acrylate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 邻二氯苯 为溶剂， 反应 3.0h， 生成 methyl 2-(3-hydroxy-1-methyl-2-oxoindolin-3-yl)acrylate
  参考文献：
  名称：

  Synthesis of dispirocyclohexadiene bisoxindole from Morita-Baylis-Hillman carbonate of isatin

  摘要：

  6 pi-Electrocyclization of conjugated trienes derived in-situ from the Morita-Baylis-Hillman carbonates of N-methylisatins afforded dispirocyclohexadiene bisoxindoles in good yields. Two stereoisomers (cis and trans) were formed in almost equal amounts. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2017.07.013

文献信息

• Synthesis of Spirocyclohexadieneyl-2-Oxindoles by 6π-Electrocyclization of Trienes Derived from Wittig Reaction of Morita-Baylis-Hillman Carbonates and α,β-Unsaturated Aldehydes
  作者：Beom Kyu Min、Da Young Seo、Ji Yeon Ryu、Junseong Lee、Jae Nyoung Kim

  DOI：10.1002/bkcs.11333

  日期：2018.1

  reported the synthesis of spirocyclohexadienyl2-oxindoles by 6π-electrocyclic ring closure (6π-ERC) of the trienes, derived from Morita-Baylis-Hillman (MBH) adducts of cinnamaldehyde and isatin (Scheme 1). Very recently, we also reported the synthesis of dispirobisoxindole from MBH carbonates of N-methylisatin (Scheme 1). During the course of our study, we decided to examine the synthesis of structurally

  螺氧吲哚存在于大量天然物质和药学上有趣的化合物中。因此，在过去的几年中，人们致力于有效的协议来访问这些重要的主题。最近，我们报道了通过肉桂醛和靛红的 Morita-Baylis-Hillman (MBH) 加合物的三烯的 6π-电环闭合 (6π-ERC) 合成螺环己二烯基 2-羟吲哚（方案 1）。最近，我们还报道了从 N-甲基靛红的 MBH 碳酸盐合成二螺双氧吲哚（方案 1）。在我们的研究过程中，我们决定通过由 N-甲基缎和肉桂醛的 MBH 碳酸盐衍生的三烯的 6π-ERC 来检查结构相关的具有不同取代模式的螺环己二烯基-2-羟吲哚的合成，如方案 1 所示。在我们的实验开始时，在 PPh3 (1.0 equiv) 存在下，在 150 C 下检查了 MBH 碳酸盐 1a 和反式肉桂醛 (2a, 1.1 equiv) 在 1,2-二氯苯 (ODCB) 中的反应。3 令我们高兴的是，在短时间内（2
• Light-Triggered Catalytic Asymmetric Allylic Benzylation with Photogenerated <i>C</i>-Nucleophiles
  作者：Suva Paria、Edoardo Carletti、Michela Marcon、Alessio Cherubini-Celli、Andrea Mazzanti、Marzio Rancan、Luca Dell’Amico、Marcella Bonchio、Xavier Companyó

  DOI：10.1021/acs.joc.0c00175

  日期：2020.3.20

  Herein is reported the asymmetric allylic benzylation of Morita-Baylis-Hillman (MBH) carbonates with 2-methylbenzophenone (MBP) derivatives as nonstabilized photogenerated C-nucleophiles. The dual activation of both reaction partners, chiral Lewis-base activation of the electrophile and light activation of the nucleophile, enables the stereoselective installation of benzyl groups at the allylic position

  本文报道了森田-贝利斯-希尔曼（MBH）碳酸酯与2-甲基二苯甲酮（MBP）衍生物作为不稳定的光生C-亲核试剂的不对称烯丙基苄基化反应。两种反应伙伴的双重激活，亲电试剂的手性路易斯碱激活和亲核试剂的光激活，使得苄基在烯丙基位置立体选择性地安装，从而形成了叔碳和季碳中心。
• Catalyst-free synthesis of 3-alkenyloxindoles from isatin-derived Morita–Baylis–Hillman carbonates
  作者：Lin Jiang、Yong-Gen Li、Hang Li、Ming-Wei Yuan、Yong-Ming Chuan、Hong-Li Li、Ming-Long Yuan

  DOI：10.3184/174751917x14878812592652

  日期：2017.3

  A variety of biologically and synthetically useful 3-alkenyloxindoles were rapidly synthesised via an S_N2′-type allylic substitution reaction of isatin-derived Morita–Baylis–Hillman carbonates with sodium sulfinates. The syntheses were conducted under catalyst-free reaction conditions and good to excellent product yields (up to 96%) and Z/E selectivities (up to >20:1) were obtained.

  通过靛红衍生的 Morita-Baylis-Hillman 碳酸酯与硫酸钠的 SN2′型烯丙基取代反应，快速合成了多种生物和合成上有用的 3-烯基吲哚。合成是在无催化剂的反应条件下进行的，获得了良好至卓越的产品收率（高达 96%）和 Z/E 选择性（高达 20:1）。
• Tertiary Amine-Catalyzed Difluoromethylthiolation of Morita-Baylis-Hillman Carbonates of Isatins with Zard's Trifluoromethylthiolation Reagent
  作者：Xing Fan、Haibin Yang、Min Shi

  DOI：10.1002/adsc.201600954

  日期：2017.1.4

  tertiary amine‐catalyzed [3+2] annulation between Morita–Baylis–Hillman (MBH) carbonates derived from isatins with thiocarbonyl fluoride (F2C=S) in situ generated from Zard's reagent proceeds smoothly under mild conditions, affording difluoromethylthiolated spirocyclic oxindoles in good to excellent yields. Moreover, the asymmetric variant could be realized with a modified Cinchona alkaloid, giving the

  在本文中，我们报道了一种新的叔胺催化的[3 + 2]环化反应，该反应是由Isards衍生的Morita–Baylis–Hillman（MBH）碳酸酯与异硫氰酸羰基氟化物（F 2 C = S）从Zard试剂原位生成的在温和的条件下，以良好或优异的收率得到二氟甲基硫醇化的螺环羟吲哚。此外，可以用修饰的金鸡纳生物碱实现不对称变体，从而以良好的对映体选择性以及良好的产率获得所需的环状加合物。
• Synthesis of spirooxindoles bearing 2,3-(or 2,5-)dihydrothiophene-2-thione moiety via [3+2] annulation of carbon disulfide with Morita-Baylis-Hillman carbonates of isatins
  作者：Beom Kyu Min、Gieun Kim、Hwa Jung Roh、Da Young Seo、Jae Nyoung Kim

  DOI：10.1016/j.tetlet.2018.03.056

  日期：2018.4

  Various spirooxindoles bearing 2,3-(or 2,5-)dihydrothiophene-2-thione moiety have been synthesized via [3+2] annulation reaction of carbon disulfide and the nitrogen ylides derived from Morita-Baylis-Hillman carbonates of isatins. 2,3-Dihydro- and 2,5-dihydrothiophene-2-thione moieties were formed selectively depending on steric hindrance around the nitrogen ylides.

  通过二硫化碳与衍生自靛红的森田-巴利斯-希尔曼碳酸盐的氮基的[3 + 2]环化反应，合成了带有2,3-（或2,5-）二氢噻吩-2-硫酮部分的各种螺硫醇。取决于氮基周围的空间位阻，选择性地形成2，3-二氢噻吩基和2，5-二氢噻吩-2-硫酮部分。