trans-4-methyl-5-phenylpyrrolidin-2-one | 138816-37-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: trans-4-methyl-5-phenylpyrrolidin-2-one
• 英文别名: (4R,5R)-4-methyl-5-phenylpyrrolidin-2-one
• CAS: 138816-37-2
• 化学式: C₁₁H₁₃NO
• 分子量: 175.23
• InChiKey: JSCZDGQZCVPSFP-LDYMZIIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2,2,2-trichloro-N-(1-phenylallyl)acetamide 在 tris(triphenylphosphine)ruthenium(II) chloride 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 、 苯 为溶剂， 反应 3.0h， 生成 trans-4-methyl-5-phenylpyrrolidin-2-one
  参考文献：
  名称：

  Transition metal catalyzed radical cyclization: new preparative route to .gamma.-lactams from allylic alcohols via the [3.3]-sigmatropic rearrangement of allylic trichloroacetimidates and the subsequent ruthenium-catalyzed cyclization of N-allyltrichloroacetamides

  摘要：

  A sequence of reactions including [3.3]-sigmatropic rearrangement of allyl trichloroacetimidates (Overman rearrangement) followed by ruthenium-catalyzed cyclization of N-allyltrichloroacetamides provided a novel method for preparing trichlorinated gamma-lactams from allylic alcohols. No delta-lactam was formed as a byproduct. The cyclization of secondary N-allyltrichloroacetamides proceeded with good diastereoselectivity. Two types of tandem cyclizations to form bicyclic lactams took place in the cyclization of N-allyltrichloroacetamides from geraniol and linalool.

  DOI：

  10.1021/jo00032a016

文献信息

• Synthetic Utility of <i>N</i>-Benzoyloxyamides as an Alternative Precursor of Acylnitrenoids for γ-Lactam Formation
  作者：Soohee Huh、Seung Youn Hong、Sukbok Chang

  DOI：10.1021/acs.orglett.9b00791

  日期：2019.4.19

  C–H amidation reaction. Upon Ir catalysis, N-benzoyloxyamides serve as efficient substrates to afford 5-membered amides. Mechanistic studies revealed that the generation of a putative Ir–carbonylnitrenoid via N–O bond cleavage is facilitated by the chelation of countercations. This protocol offers a convenient and step-economic route to γ-lactams starting from the corresponding carboxylic acids.

  本文描述的是通过分子内C–H酰胺化反应合成用于γ-内酰胺的酰基类肾上腺素前体的新开发。在Ir催化下，N-苯甲酰氧基酰胺可作为有效的底物，提供5元酰胺。机理研究表明，抗衡阳离子的螯合促进了通过N-O键裂解生成假定的Ir-羰基类肾上腺素。该方案提供了从相应的羧酸开始制备γ-内酰胺的便捷且经济的途径。
• Harnessing Secondary Coordination Sphere Interactions That Enable the Selective Amidation of Benzylic C–H Bonds
  作者：Hoimin Jung、Malte Schrader、Dongwook Kim、Mu-Hyun Baik、Yoonsu Park、Sukbok Chang

  DOI：10.1021/jacs.9b07795

  日期：2019.9.25

  site-selectivity is highly desirable especially in C-H functionalization reactions. We report a new catalyst platform that is highly selective for the amidation of benzylic C-H bonds controlled by π-π interactions in the secondary coordination sphere. Mechanistic understanding of the previously developed iridium catalysts that showed poor regioselectivity gave rise to the recognition that the π-cloud

  工程位点选择性是非常需要的，尤其是在 CH 官能化反应中。我们报告了一种新的催化剂平台，该平台对由二级配位球中的 π-π 相互作用控制的苄基 CH 键的酰胺化具有高度选择性。对先前开发的铱催化剂显示出较差的区域选择性的机理理解引起了这样的认识，即基底上芳香族片段的 π 云可以通过与催化剂的双齿配体的有吸引力的非共价相互作用充当正式的导向基团. 基于这种机制驱动的策略，我们开发了一种带有中性多吡啶基配体的阳离子 (η5-C5H5)Ru(II) 催化剂，在同时存在叔 CH 键的情况下，在分子内 CH 内酰胺化中获得了创纪录的苄选择性。距离。结合实验和计算技术来确定这种前所未有的苄基选择性的起源，并且发现溶剂极性指数和测得的位点选择性之间稳健的线性自由能关系清楚地证实了疏溶剂效应驱动了选择性。证明了反应范围的普遍性和对多功能 γ-内酰胺合成的适用性。
• Selective formation of γ-lactams via C–H amidation enabled by tailored iridium catalysts
  作者：Seung Youn Hong、Yoonsu Park、Yeongyu Hwang、Yeong Bum Kim、Mu-Hyun Baik、Sukbok Chang

  DOI：10.1126/science.aap7503

  日期：2018.3.2

  this rearrangement, steering the nitrene toward C–H insertion to form a variety of useful lactam rings. Science, this issue p. 1016 Theory guides design of a catalyst to cyclize amides via a nitrene intermediate otherwise prone to a competing rearrangement. Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form γ-lactam rings has traditionally been hindered by competing isocyanate

  引导氮烯远离迁移 氮通常与一个或多个伙伴以三个键共享其电子。单键氮或氮烯具有异常的反应性，可以将自身插入通常惰性的 C-H 键中。但是，如果氮烯在羰基中心旁边形成，它往往会与另一侧的 C-C 键反应。洪等人。使用理论来指导抑制这种重排的铱催化剂的设计，引导氮烯向 C-H 插入以形成各种有用的内酰胺环。科学，这个问题 p。1016 理论指导设计催化剂以通过氮烯中间体环化酰胺，否则容易发生竞争性重排。金属氮烯分子内插入碳氢键形成γ-内酰胺环传统上受到异氰酸酯竞争形成的阻碍。我们报告了应用理论和机理研究来优化一类五甲基环戊二烯基铱 (III) 催化剂以抑制这种竞争途径。密度泛函理论计算表明，将辅助双齿配体的立体电子特性调节为更多的电子供体，以降低有利于所需反应的 C-H 插入势垒。这些催化剂可通过 sp3 和 sp2 C-H 酰胺化以优异的选择性将各种 1,4,2-二恶唑-5-酮、羰基硝基苯前体从羧酸中容易地转化为相应的
• Metal complex, method for producing same, and method for producing gamma-lactam compound using same
  申请人：INSTITUTE FOR BASIC SCIENCE

  公开号：US11344872B2

  公开（公告）日：2022-05-31

  The present invention relates to a novel metal complex, a method for producing same, and a method for producing a gamma-lactam compound using same, and the metal complex according to the present invention is used as a catalyst for producing a gamma-lactam compound and can efficiently produce a gamma-lactam compound with an excellent yield and excellent selectivity.

  本发明涉及一种新型金属配合物、其制备方法以及使用该金属配合物制备γ-内酰胺化合物的方法。本发明的金属配合物用作制备γ-内酰胺化合物的催化剂，能够高效地产生具有优异收率和选择性的γ-内酰胺化合物。
• NOVEL METAL COMPLEX, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING GAMMA-LACTAM COMPOUND USING SAME
  申请人：INSTITUTE FOR BASIC SCIENCE

  公开号：US20200330969A1

  公开（公告）日：2020-10-22

  The present invention relates to a novel metal complex, a method for producing same, and a method for producing a gamma-lactam compound using same, and the metal complex according to the present invention is used as a catalyst for producing a gamma-lactam compound and can efficiently produce a gamma-lactam compound with an excellent yield and excellent selectivity.