(3R,9bS)-3-Phenyl-2,3,5,9b-tetrahydro[1,3]oxazolo[2,3-a]isoindol-5-one | 191531-86-9

• 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
• 英文名称: (3R,9bS)-3-Phenyl-2,3,5,9b-tetrahydro[1,3]oxazolo[2,3-a]isoindol-5-one
• 英文别名: trans-(3R,9bS)-3-phenyl-2,3-dihydro-9bH-oxazolo[2,3-a]isoindol-5-one；(3R,9bS)-3-phenyl-2,3-dihydrooxazolo[2,3-a]isoindol-5(9bH)-one；(3R,9bS)-3-phenyl-3,9b-dihydro-2H-[1,3]oxazolo[2,3-a]isoindol-5-one
• CAS: 191531-86-9
• 化学式: C₁₆H₁₃NO₂
• 分子量: 251.285
• InChiKey: LWFJSVCUHMPYEM-HOCLYGCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,9bS)-3-Phenyl-2,3,5,9b-tetrahydro[1,3]oxazolo[2,3-a]isoindol-5-one 在 盐酸 、 乙醇 、 三氟甲磺酸三甲基硅酯 、 sodium ethanolate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 3-allylisoindolin-1-one
  参考文献：
  名称：

  A new approach to the synthesis of non-racemic isoindolin-1-one derivatives

  摘要：

  A new approach for the synthesis of non-racemic 3-substituted isoindolin-1-one targets has been developed through application of a tricyclic gamma-lactam substrate as an N-acyliminium ion precursor. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)80041-5
• 作为产物：
  描述：

  邻羧基苯甲醛 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 72.25h， 生成 (3R,9bS)-3-Phenyl-2,3,5,9b-tetrahydro[1,3]oxazolo[2,3-a]isoindol-5-one
  参考文献：
  名称：

  在温和的高立体选择性条件下，迈耶斯的双环内酰胺形成

  摘要：

  本文报道了以高产率和高非对映选择性制备手性双环内酰胺的新的温和条件。这种基于Mukaiyama试剂对羧酸进行活化的方法是Meyers脱水条件的极佳替代方法，并提供了在较低温度（40°C）下工作的主要优势。用5,7-双环内酰胺获得更高的非对映选择性（标准脱水条件下，de = 82％，而不是44％）。

  DOI：

  10.1016/j.tetlet.2005.09.154

文献信息

• A novel and highly stereoselective route for the synthesis of non-racemic 3-substituted isoindolin-1-one targets
  作者：Ryan A. Hemming、Megan Bell、Liam J. Duffy、Jonathan Bristow、John D. Wallis、Steven M. Allin、Philip C. Bulman Page

  DOI：10.1016/j.tet.2018.11.050

  日期：2019.1

  A new, versatile and highly stereoselective approach for the synthesis of non-racemic 3-substituted isoindolin-1-ones is described from a readily available chiral template. The potential of this new protocol is demonstrated through the synthesis of an enantiomerically enriched 3-alkyl N-H isoindolin-1-one target with an e.e. of 98%.

  从容易获得的手性模板中描述了用于合成非外消旋的3-取代的异吲哚啉-1-酮的新的，通用的和高度立体选择性的方法。通过合成对映体富集的3-烷基N - H异吲哚啉-1-酮靶标，其ee为98％，证明了该新方案的潜力。
• Approaches to the synthesis of non-racemic 3-substituted isoindolinone derivatives
  作者：Steven M. Allin、Christopher J. Northfield、Michael I. Page、Alexandra M. Z. Slawin

  DOI：10.1039/b001569p

  日期：——

  New methodology for the synthesis of non-racemic isoindolinone targets has been developed through application of tricyclic γ-lactam substrates as N-acyliminium ion precursors in reactions with carbon and hydride nucleophiles. Removal of the phenylglycinol derived chiral auxiliary can be achieved without loss of stereochemical integrity at the newly created asymmetric centre, and we report a novel method for this key step using conc. sulfuric acid.

  通过在碳和氢化物亲核试剂反应中应用三环γ-内酰胺底物作为N-酰基亚胺离子前体，已经开发出一种合成非外消旋异吲哚酮目标的新方法。可以从新形成的不对称中心移除由苯基甘氨酸衍生的手性辅助剂，而不会损失立体化学完整性，并且我们报道了一种使用浓硫酸实现这一关键步骤的新方法。
• A highly diastereoselective synthesis of tricyclic lactams and their application as novel N-acyl iminium ion precursors in the synthesis of isoindolinone derivatives
  作者：Steven M Allin、Christopher J Northfield、Michael I Page、Alexandra M.Z Slawin

  DOI：10.1016/s0040-4039(97)00686-2

  日期：1997.5

  extremely high diastereoselectivity to produce tricyclic γ-lactam products. The relative stereochemistry of the major diastereoisomer has been determined by X-ray crystal analysis and a mechanism suggested to explain the stereochemical outcome. Further, we report that this class of heterocycle can act as an N-acyl iminium ion precursor in the synthesis of substituted isoindolinone derivatives.

  2-甲酰基苯甲酸与α-氨基醇底物的缩合以极高的非对映选择性进行，以产生三环γ-内酰胺产物。主要的非对映异构体的相对立体化学已通过X射线晶体分析确定，并提出了解释立体化学结果的机理。此外，我们报道，这类杂环可以在取代的异吲哚满酮衍生物的合成中充当N-酰基亚胺鎓离子的前体。
• Multimetallic Iridium-Tin (Ir-Sn₃) Catalyst in<i>N</i>-Acyliminium Ion Chemistry: Synthesis of 3-Substituted Isoindolinones<i>via</i>Intra- and Intermolecular Amidoalkylation Reaction
  作者：Arnab Kumar Maity、Sujit Roy

  DOI：10.1002/adsc.201400234

  日期：2014.8.11

  AbstractThe multimetallic iridium‐tritin (Ir‐Sn3) complex [Cp*Ir(SnCl3)2SnCl2(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