3-hydroxy-3-(1-methyl-propa-1,2-dienyl)-1,3-dihydro-indol-2-one | 851663-56-4

• 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: 3-hydroxy-3-(1-methyl-propa-1,2-dienyl)-1,3-dihydro-indol-2-one
• 英文别名: 3-allenyl 3-hydroxyindolin-2-one
• CAS: 851663-56-4
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: UMPTZDBSHXVMFX-UHFFFAOYSA-N

物化性质

• 熔点：
  179-180 °C(Solv: hexane (110-54-3); ethyl acetate (141-78-6))
• 沸点：
  409.6±45.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-hydroxy-3-(1-methyl-propa-1,2-dienyl)-1,3-dihydro-indol-2-one 在 iron(III) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以70%的产率得到(3Z)-3-(3-chlorobut-3-en-2-ylidene)-1H-indol-2-one
  参考文献：
  名称：

  Direct FeX₃-Based Stereocontrolled Access to (Z)-3-Alkenyl-oxindoles from Allenols

  摘要：

  Iron trihalides (FeCl3 and FeBr3) smoothly promote the halogenation/rearrangement of 2-indolinone-tethered allenols to efficiently afford 3-halodienyl-oxindoles with good yield and total selectivity. Also, 2-halo-1,3-dienes are synthetically interesting building blocks for the preparation of functionalized 3-alkenyl-oxindoles through a Suzuki-Miyaura reaction.

  DOI：

  10.1021/jo302296r
• 作为产物：
  描述：

  靛红 、 1-溴-2-丁炔 在 indium 、 氯化铵 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 3-hydroxy-3-(1-methyl-propa-1,2-dienyl)-1,3-dihydro-indol-2-one
  参考文献：
  名称：

  Metal-catalyzed rearrangements of 3-allenyl 3-hydroxyindolin-2-ones in the presence of halogenated reagents

  摘要：

  研究人员探讨了 3-烯基 3-羟基吲哚与多种卤代试剂在催化量贵金属盐存在下的反应。重排反应和氧环化反应分别生成 4-（1-卤乙烯基）-喹啉二酮或螺环卤代吲哚，这两种反应都是竞争性途径。官能化的种类取决于底物和反应条件。

  DOI：

  10.1039/c2ob27359d

文献信息

• Gold-Photoredox-Cocatalyzed Tandem Oxycyclization/Coupling Sequence of Allenols and Diazonium Salts with Visible Light Mediation
  作者：Benito Alcaide、Pedro Almendros、Borja Aparicio、Carlos Lázaro-Milla、Amparo Luna、Olalla Nieto Faza

  DOI：10.1002/adsc.201700598

  日期：2017.8.17

  The room temperature radical cycloetherification/arylation cascade of allenols and diazonium salts has been accomplished via a combination of gold and photoredox catalysis to provide 2,3,4‐trisubstituted‐2,5‐dihydrofurans. The functionalized oxacycle formation sequence is chemo‐ and regioselective for the cycloetherification and for the position that bears the aryl moiety after the cross‐coupling.

  烯醇和重氮盐的室温自由基环醚化/芳基化级联反应已通过金和光氧化还原催化的组合完成，从而提供了2,3,4-三取代-2,5-二氢呋喃。功能化的氧杂环形成序列对环醚化以及交叉偶联后带有芳基部分的位置具有化学和区域选择性。机理研究表明，这种转变是通过金（I）初始氧化为苯基金（III）配合物而进行的，该配合物与烯丙基配位后，催化其环化并在还原消除后生成偶联产物，从而生成金（I） ）。
• Controlled Rearrangement of Lactam-Tethered Allenols with Brominating Reagents: A Combined Experimental and Theoretical Study on α- versus β-Keto Lactam Formation
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、Sara Cembellín、Manuel Arnó、Luis R. Domingo

  DOI：10.1002/chem.201101160

  日期：2011.10.4

  expansion of lactam‐tethered allenols to efficiently afford cyclic α‐ or β‐ketoamides with good yields and high chemo‐, regio‐, and diastereoselectivity, through controlled CC bond cleavage of the β‐ or γ‐lactam nucleus. Interestingly, in contrast to the rearrangement reactions of 2‐azetidinone‐tethered allenols, which lead to the corresponding tetramic acid derivatives (β‐keto lactam adducts) as the

  Ñ溴代琥珀酰亚胺（NBS）顺利促进内酰胺拴allenols的环扩展以有效地得到环状α-或β酮酰胺具有良好的产率和高的化学-选择性，区域选择性和非对映选择性，通过控制Ç 的β的C键裂解γ或γ-内酰胺核。有趣的是，与2-氮杂环丁酮-系留的烯丙醇的重排反应形成唯一的产物相应的四酸衍生物（β-酮内酰胺加合物）相反，在相似条件下2-吲哚酮-系留的烯丙醇的反应产生了喹啉。 -2,3-二酮（α-酮内酰胺加成物）作为独家产品或主要产品。为了使实验观察合理化，已经进行了理论研究。
• Ring Enlargement versus Selenoetherification on the Reaction of Allenyl Oxindoles with Selenenylating Reagents
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、Gonzalo Gómez-Campillos、M. Rosario Torres

  DOI：10.1021/jo202495z

  日期：2012.4.6

  Lactam-tethered allenols, readily prepared from α-oxolactams, were used as starting materials for divergent reactivity with selenenylating reagents. Either oxycyclization (spirocyclic selenolactams) or ring expansion (selenoquinolones) can be achieved through the choice of both reagents and substrates. The biological activity of some of the synthesized heterocycles has additionally been evaluated in four human

  容易由α-氧代内酰胺制备的内酰胺束缚的烯丙醇用作起始原料，用于与硒烯化试剂发生发散反应。氧环化（螺环硒内酰胺）或环扩环（硒代喹诺酮）均可通过选择试剂和底物来实现。另外，已经在四种人类癌细胞系中评估了某些合成杂环的生物活性。
• An Alternative to Precious Metals: Hg(ClO₄)₂·3H₂O as a Cheap and Water-Tolerant Catalyst for the Cycloisomerization of Allenols
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、Elena Soriano

  DOI：10.1021/acs.joc.5b00887

  日期：2015.7.17

  Hg(ClO4)(2)center dot 3H(2)O, a cheap, water-tolerant, and stable salt, catalyzes the cydoisomerization reaction or alpha-allenols to 2,5-dihydrofurans in an efficient and selective manner. The reaction is general and can be applied to differently functionalized substrates, including alkyl-substituted, aryl-substituted, enantiopure, and tertiary allenols. In addition, density functional theory (DFT) calculations were performed to obtain insight into various aspects of the controlled reactivity of a-allenols under mercury catalysis. They suggest a dual activation of the allenol by the Hg complex that drives the reaction to the chemoselective formation of 2,5-dihydrofurans.
• Efficient Entry to Diversely Functionalized Spirocyclic Oxindoles from Isatins through Carbonyl-Addition/Cyclization Reaction Sequences
  作者：Benito Alcaide、Pedro Almendros、Raquel Rodríguez-Acebes

  DOI：10.1021/jo0525027

  日期：2006.3.1

  A novel approach to diversely functionalized spirocyclic oxindoles has been developed by using different metal-mediated carbonyl-addition/cyclization reaction sequences. Spirocyclization precursors, 2-indolinonetethered homoallylic alcohols, (buta-1,3-dien-2-yl)methanols, and alpha-allenols have been obtained by regioselective addition of stabilized organoindium reagents to isatins in aqueous environment. Ruthenium-, silver-, and palladium-catalyzed reactions of the above unsaturated alcohol derivatives provided oxaspiro oxindoles.