3,3-二甲基-2-苯基异吲哚-1-酮 | 53890-83-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 中文名称: 3,3-二甲基-2-苯基异吲哚-1-酮
• 英文名称: 2-phenyl-3,3-dimethylisoindoline-1-one
• 英文别名: 3,3-dimethyl-2-phenylisoindolin-1-one；3,3-Dimethyl-N-phenylphthalimidine；3,3-dimethyl-2-phenyl-2,3-dihydro-isoindol-1-one；3,3-Dimethyl-2-phenyl-isoindolin-1-on；3,3-Dimethyl-2-phenylisoindol-1-one
• CAS: 53890-83-8
• 化学式: C₁₆H₁₅NO
• 分子量: 237.301
• InChiKey: GBIGLHDPTGVTGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3-二甲基-2-苯基异吲哚-1-酮 在 劳森试剂 作用下， 以 甲苯 为溶剂， 生成 2-phenyl-3,3-dimethylisoindoline-1-thione
  参考文献：
  名称：

  Photoreactions of isoindoline-1-thiones with alkenes: unusual formation of tricyclic isoindolines

  摘要：

  Photochemical cycloaddition reactions of cyclic thioamides and alkenes have been examined. Irradiation of 2-arylisoindoline-1-thiones 1 in the presence of alkenes 2 gave the unexpected tricyclic isoindolines 3-18. The formation of tricyclic isoindolines can best be explained in terms of the intermediacy of aminospirothietane 27, formed by [2 + 2] photocycloaddition of the C=S double bond of 1 to the C=C double bond of 2. Ring cleavage of the resultant amino thietane, assisted by the participation of the nitrogen lone-pair electrons, produced zwitterions 28 and 29 or 1-mercaptoethylisoindole (30). Subsequent nucleophilic attack of the thiol anion on the iminium carbon of 29 or attack of the thiol group on C-3 of 30 gave the final products. Irradiation of isobenzofuran-1-thione (22) and isobenzothiophene-l-thione (23) in the presence of tetramethylethylene (2a) gave the corresponding spirothietanes 24 and 25.

  DOI：

  10.1021/jo00040a049
• 作为产物：
  描述：

  2-(2-溴苯基)-2-丙醇 在 盐酸 、 正丁基锂 作用下， 反应 7.5h， 生成 3,3-二甲基-2-苯基异吲哚-1-酮
  参考文献：
  名称：

  Selective halogen-lithium exchange in some secondary and tertiary (bromophenyl)alkyl halides

  摘要：

  DOI：

  10.1021/jo00336a043

文献信息

• KO^<i>t</i>Bu-Mediated Synthesis of Dimethylisoindolin-1-ones and Dimethyl-5-phenylisoindolin-1-ones: Selective C–C Coupling of an Unreactive Tertiary sp³ C–H Bond
  作者：Bhagat Singh Bhakuni、Abhimanyu Yadav、Shailesh Kumar、Saket Patel、Shubham Sharma、Sangit Kumar

  DOI：10.1021/jo402776u

  日期：2014.4.4

  dihalobenzamides for the synthesis of biaryl 5-phenylisoindolin-1-ones. It seems that the reaction proceeds via a radical pathway in which the aryl radical translocates via 1,5-hydrogen atom transfer (HAT), forming a tertiary alkyl carbon-centered radical. The generated tertiary alkyl radical could attack the benzamide ring in a 5-exo/endo-trig manner followed by the release of an electron and a proton, leading to

  由2-卤代-N-异丙基-N-烷基苯甲酰胺底物和KO t Bu通过不反应的叔sp 3 C-H键的选择性CC偶联，提出了一种合成二甲基异吲哚啉酮的新反应。该反应对伯或秒的sp 3 C–H叔键表现出优异的选择性碳氢键。此外，使用二卤代苯甲酰胺合成联芳基5-苯基异吲哚-1-酮可以在一锅中实现联芳基CC偶联和烷基芳基CC偶联。看来反应是通过自由基途径进行的，其中芳基通过1，5-氢原子转移（HAT）转移，形成以叔烷基碳为中心的自由基。产生的叔烷基可以5-外/内触发方式攻击苯甲酰胺环，随后释放电子和质子，从而形成五元异吲哚啉酮环。HAT似乎负责叔烷基在伯和仲CH键上的选择性官能化。
• Palladium-Catalyzed Oxidative Activation of Arylcyclopropanes
  作者：Zhi He、Andrei K. Yudin

  DOI：10.1021/ol062476e

  日期：2006.12.1

  Palladium chloride-catalyzed intramolecular activation of electroneutral cyclopropane derivatives results in cleavage of the cyclopropane ring followed by formation of heterocyclic derivatives. Phenols, carboxylic acids, and amide groups were considered as substituents ortho to the cyclopropane ring in this catalytic activation chemistry. The regioselectivity observed in the case of amide-containing

  电中性环丙烷衍生物的氯化钯催化的分子内活化导致环丙烷环的裂解，随后形成杂环衍生物。在该催化活化化学中，酚，羧酸和酰胺基被认为是环丙烷环邻位的取代基。在含酰胺的底物的情况下观察到的区域选择性与含羧酸的底物的区域选择性不同，排除了简单的环丙烷异构化，然后进行瓦克氧化作为机理途径。[反应：看文字]
• Hydriodic Acid-Mediated Cyclization of α-Substituted Secondary 2-Ethenylbenzamides: Synthesis of 2-Substituted 2,3-Dihydro-3,3-dimethyl-1H-isoindol-1-ones and 3,3-Disubstituted (E)-1-(Arylimino)-1,3-dihydroisobenzofurans
  作者：Kazuhiro Kobayashi、Seiki Fujita、Daisuke Nakai、Shogo Fukumoto、Shuhei Fukamachi、Hisatoshi Konishi

  DOI：10.1002/hlca.201000172

  日期：——

  for the preparation of 2‐substituted 2,3‐dihydro‐3,3‐dimethyl‐1H‐isoindol‐1‐ones 3 and 3,3‐disubstituted (E)‐1‐(arylimino)‐1,3‐dihydroisobenzofurans 6 has been developed. Thus, treatment of N‐alkyl(or aryl)‐2‐(1‐methylethen‐1‐yl)benzamides 2 with concentrated hydriodic acid (HI) in MeCN at room temperature afforded 3. Similar treatment of N‐aryl‐2‐(1‐phenylethen‐1‐yl)benzamide 5 with concentrated HI

  一种新的简便方法，可制备2-取代的2,3-二氢-3,3-二甲基-1 H-异吲哚-1-酮3和3,3-二取代（E）-1（芳基）-1已经开发了3-3-二氢异苯并呋喃6。因此，治疗的ñ -烷基（或芳基）-2-（1- methylethen -1-基）苯甲酰胺2与在MeCN浓氢碘酸（HI）在得到室温下3。在0°下用浓HI对N-芳基-2-（1-苯基乙-1-基）苯甲酰胺5进行类似处理，得到6。
• Synthesis of 3,3-Disubstituted Isoindolin-1-ones via Iodoamination of α-Substituted Secondary 2-Vinylbenzamides
  作者：Kazuhiro Kobayashi、Masanori Hase、Kenichi Hashimoto、Seiki Fujita、Miyuki Tanmatsu、Osamu Morikawa、Hisatoshi Konishi

  DOI：10.1055/s-2006-942462

  日期：2006.8

  A new and simple method for the preparation of 3,3-di­substituted isoindolin-1-ones from α-substituted 2-bromostyrenes is described. Construction of the isoindolin-1-one skeleton was accomplished by treating α-substituted secondary 2-vinylbenzamides, easily obtainable from the reaction of α-substituted 2-lithiostyrenes with isocyanates, with iodine to afford 3-substituted 3-iodomethylisoindolin-1-ones.

  本文介绍了一种从δ±-取代的 2-溴苯乙烯制备 3,3-二取代异吲哚啉-1-酮的简单新方法。δ-取代的仲2-乙烯基苯甲酰胺很容易从δ-取代的2-硫代苯乙烯与异氰酸酯的反应中获得，通过用碘处理δ-取代的仲2-乙烯基苯甲酰胺，得到3-取代的3-碘甲基异吲哚啉-1-酮，从而构建了异吲哚啉-1-酮的骨架。
• Rhodium-Catalyzed Asymmetric (3 + 2 + 2) Annulation <i>via</i> N–H/C–H Dual Activation and Internal Alkyne Insertion toward <i>N</i>-Fused 5/7 Bicycles
  作者：Chao Yang、Lijun Shi、Fang Wang、Yijin Su、Ji-Bao Xia、Fuwei Li

  DOI：10.1021/acscatal.2c04373

  日期：2022.11.18

  report rhodium-catalyzed (3 + 2 + 2) annulation of alkenylamides with alkynes for the efficient synthesis of stereogenic 1-azabicyclo[5.3.0]decanes through N–H/C–H bond dual activation. Moreover, the corresponding asymmetric catalytic reaction has been realized leading to enantioenriched products bearing bridgehead quaternary stereocenter in moderate-to-good yields with up to 96% ee. Mechanistic studies

  N-稠合 5/7 元自行车在许多生物活性分子中具有明显的重要性，但由于不利的空间位阻、跨环相互作用和拥挤的桥头立构中心，很少有通过不对称催化构建这些特殊支架的例子。我们在此报道了铑催化的烯基酰胺与炔烃的 (3 + 2 + 2) 环化反应，通过 N-H/C-H 键双重活化有效合成立体异构 1-氮杂双环 [5.3.0] 癸烷。此外，相应的不对称催化反应已经实现，导致具有桥头四元立构中心的对映体富集产物以中等至良好的收率和高达 96% ee 的收率。机理研究和密度泛函理论计算表明，铑经历了预设的独特催化途径通过栓系烯的氨基铑化产生立体异构的烷基-Rh 物种，其经历以下 C-H 活化和炔烃插入以提供关键的 8 元 rhodacycle 中间体。该协议公开了一种非常有价值的不对称铑介导的 C-H 功能化模式，并验证了手性 1-氮杂双环 [5.3.0] 癸烷的从头级联构造。