2-allyl-3-(1-benzoyl-2-oxo-2-phenyl-ethyl)-2,3-dihydro-isoindol-1-one | 1215178-33-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2-allyl-3-(1-benzoyl-2-oxo-2-phenyl-ethyl)-2,3-dihydro-isoindol-1-one
• 英文别名: 2-allyl-3-(1-benzoyl-2-oxo-2-phenylethyl)-2,3-dihydroisoindol-1-one；2-(2-allyl-3-oxoisoindolin-1-yl)-1,3-diphenylpropane-1,3-dione
• CAS: 1215178-33-8
• 化学式: C₂₆H₂₁NO₃
• 分子量: 395.458
• InChiKey: RMHLJKMXGVELNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  30.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  54.45
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  苯酐 在 甲醇 、 sodium tetrahydroborate 、 C₁₀H₁₉Cl₈IrO₂Sn₃ 、 三乙胺 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 38.0h， 生成 2-allyl-3-(1-benzoyl-2-oxo-2-phenyl-ethyl)-2,3-dihydro-isoindol-1-one
  参考文献：
  名称：

  N-酰基亚胺离子化学中的多金属铱锡（Ir-Sn 3）催化剂：通过分子内和分子间酰胺基烷基化反应合成3-取代的异吲哚满酮

  摘要：

  AbstractThe multimetallic iridium‐tritin (Ir‐Sn3) complex [Cp*Ir(SnCl3)2{SnCl2(H2O)2}] (1) proved to be a highly effective catalyst towards COH bond activation of γ‐hydroxylactams, leading to a nucleophilic substitution reaction known as the α‐amidoalkylation reaction. Catalyst 1 can be easily synthesized from the reaction of (pentamethylcyclocyclopentadienyl)iridium dichloride dimer {[Cp*IrCl2]2} and tin(II) dichloride (SnCl2). In terms of catalyst loading, reaction conditions and yields of the product formed, 1 is found to be superior compared to classical Lewis acid catalysts. Different carbon (arenes, heteroarenes, allyltrimethylsilane, 1,3‐dicarbonyls) and heteroatom (alcohols, thiols, amides and sulfonamides) nucleophiles have been successfully employed in the intramolecular and intermolecular alkylations, as well as in heterocyclization reactions. In the majority of cases good to excellent yields of 3‐substituted isoindolinones and 5‐substituted pyrrolidin‐2‐ones have been obtained. Besides, the reactions are also atom economical and salt free. It is proposed that the multimetallic Ir‐Sn3 catalyst behaves as a mild and selective Lewis acid to activate the γ‐hydroxylactam towards the formation of the N‐acyliminium ion; the latter being trapped by potent nucleophiles leading to the desired products.magnified image

  DOI：

  10.1002/adsc.201400234

文献信息

• N-Acyliminium Ion Chemistry: Highly Efficient and Versatile Carbon-Carbon Bond Formation by Nucleophilic Substitution of Hydroxy Groups Catalyzed by Sn(NTf2)4
  作者：Raja Ben Othman、Radouane Affani、Marie-José Tranchant、Sylvain Antoniotti、Vincent Dalla、Elisabet Duñach

  DOI：10.1002/anie.200906036

  日期：2010.1.18

  O‐acetals are used in a catalytic, highly efficient α‐amidoalkylation of a broad range of carbon‐centered nucleophiles, including silicon‐based components, active methylene derivatives, electron‐rich arenes, and even simple ketones (see scheme). The reactions proceed in a highly efficient manner and typically require only 1 mol % of the Lewis superacidic reagent Sn(NTf2)4 as the catalyst.

  原子经济：未经修饰的半-N，O-乙缩醛可用于各种以碳为中心的亲核试剂的高效催化α-酰胺基烷基化反应，包括硅基组分，活性亚甲基衍生物，富电子芳烃，甚至简单的酮（见方案）。反应以高效的方式进行，并且通常仅需要1mol％的路易斯超酸性试剂Sn（NTf 2）4作为催化剂。
• Intra- and Intermolecular Alkylation of <i>N</i>,<i>O</i>-Acetals and π-Activated Alcohols Catalyzed by in Situ Generated Acid
  作者：Mélanie Hamon、Niall Dickinson、Alice Devineau、David Bolien、Marie-José Tranchant、Catherine Taillier、Ivan Jabin、David C. Harrowven、Richard J. Whitby、A. Ganesan、Vincent Dalla

  DOI：10.1021/jo4015886

  日期：2014.3.7

  allow significant reaction rate enhancements and made possible some challenging reactions such as the α-amidoalkylation of ketones. Studies using flow chemistry confirmed not only that very low concentrations of HCl generated from the solvent were responsible for the reactivity but also that TCE had additional beneficial properties in comparison to other chlorinated solvents such as dichloroethane.

  电离能力有限的碳正离子前体的分子内和分子间烷基化，主要是N，O已经开发了不使用外源试剂的-乙缩醛。反应在1,1,2,2-四氯乙烷（TCE）中进行，并利用该溶剂通过热解消除连续释放少量HCl的能力。对反应的研究导致了几种改进的方案，例如（1）预热的TCE，（2）微波辅助反应和（3）流动或密闭管条件，这些条件可以显着提高反应速率，并使得某些具有挑战性的反应成为可能。作为酮的α-酰胺基烷基化。使用流动化学的研究证实，不仅由溶剂产生的极低浓度的HCl负责反应，而且与其他氯化溶剂（如二氯乙烷）相比，TCE还具有其他有益的性能。该方法可以很容易地扩展到使用亲电试剂（如π活化的醇）进行烷基化反应，这些亲电子试剂通常对HCl催化不反应。这项工作代表了最成功的最简单的布朗斯台德酸HCl作为有效的烷基化催化剂的首次成功使用。
• One-Pot Hydroxy Group Activation/Carbon-Carbon Bond Forming Sequence Using a Brønsted Base/Brønsted Acid System
  作者：Alice Devineau、Guillaume Pousse、Catherine Taillier、Jérôme Blanchet、Jacques Rouden、Vincent Dalla

  DOI：10.1002/adsc.201000602

  日期：2010.11.22

  distinct feature of the trichloroacetimidate group allows use of weaker acid catalysts such as 1,1′-bi-2-naphthol (BINOL)-derived phosphoric acid, pointing out the possible development of an enantioselective variant. This unprecedented sequential one-pot Brønsted base-Brønsted acid catalysis further expands the synthetic scope of the trichloroacetimidate group.

  提出了一种新的连续两步多催化策略，该策略包括有效的DBU催化的醇的三氯乙酰亚胺化，然后由硅基亲核试剂和CH亲核试剂进行双三氟乙胺（Tf 2 NH）催化的分子间烷基化。三氯乙酰基亚氨酸酯基团的独特特征允许使用弱酸催化剂，例如1,1'-联-2-萘酚（BINOL）衍生的磷酸，指出了对映选择性变体的可能发展。这种前所未有的连续一锅法布朗斯台德碱布朗斯台德酸催化进一步扩大了三氯乙酰亚胺基的合成范围。