((E)-4-but-1-enyl)-oxazolidin-2-one | 917908-13-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: ((E)-4-but-1-enyl)-oxazolidin-2-one
• 英文别名: (E)-4-(but-1-en-1-yl)oxazolidin-2-one；4-[(E)-but-1-enyl]-1,3-oxazolidin-2-one
• CAS: 917908-13-5
• 化学式: C₇H₁₁NO₂
• 分子量: 141.17
• InChiKey: OATSGBKJUGFTBP-ONEGZZNKSA-N

物化性质

• 沸点：
  312.5±22.0 °C(Predicted)
• 密度：
  1.132±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-hex-3-en-1-yl [{3,5-bis(trifluoromethyl)benzoyl}oxy]carbamate 在 tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate 、 potassium carbonate 作用下， 以 1,1,2,2-四氯乙烷 为溶剂， 反应 12.0h， 以63%的产率得到((E)-4-but-1-enyl)-oxazolidin-2-one
  参考文献：
  名称：

  调节异羟肟酸酯作为分子内 C(sp3)-H 酰胺化的氮烯前体的三重态能量转移

  摘要：

  本文报道了产生三线态氮烯的光敏化策略的设计及其在分子内 CH 酰胺化反应中的适用性。通过根据提议的能量转移途径调整物理有机参数来优化基材，使我们将异羟肟酸盐鉴定为一种方便的氮烯前体。虽然更经典的氮烯来源，以有机叠氮化物为代表，在当前的光敏化条件下无效，但容易从醇或羧酸中获得的异羟肟酸酯在通过可见光获取具有合成价值的 2-恶唑烷酮和 γ-内酰胺方面非常有效。机理研究支持了我们的工作假设，即能量转移路径主要是有效的。

  DOI：

  10.1021/jacs.0c00868

文献信息

• Chemo‐ and Enantioselective Intramolecular Silver‐Catalyzed Aziridinations
  作者：Minsoo Ju、Cale D. Weatherly、Ilia A. Guzei、Jennifer M. Schomaker

  DOI：10.1002/anie.201704786

  日期：2017.8.7

  nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and

  不对称的腈转移反应是制备对映体丰富的胺结构单元的有力工具。本文报道的是化学选择性和对映选择性银催化的胺化反应，它们可以将二和三取代的氨基甲酸氨基甲酸酯以高收率转化为[4.1.0]-氨基甲酸酯连接的氮丙啶，ee值最高为92％。探索了底物，抗衡银，配体，溶剂和温度对化学选择性和ee值的影响。提出了立体化学模型以合理化所观察到的氮丙啶的绝对立体化学，所述氮丙啶经过亲核开环以产生对映体富集的胺，而立体化学完整性没有受到侵蚀。
• Rh(ii)-catalysed room temperature aziridination of homoallyl-carbamates
  作者：Christopher J. Hayes、Peter W. Beavis、Lesley A. Humphries

  DOI：10.1039/b611662k

  日期：——

  Rhodium(II) catalysts and PhIO in benzene convert homoallylic carbamates into the corresponding aziridines at room temperature.

  铑（II）催化剂和 PhIO 在苯中可在室温下将均质烯丙基氨基甲酸酯转化为相应的氮丙啶。
• Solvent Effects on the Chemo‐ and Site‐Selectivity of Transition Metal‐Catalyzed Nitrene Transfer Reactions: Alternatives to Chlorinated Solvents**
  作者：Robert M. Ward、Yun Hu、Noah P. Tu、Jennifer M. Schomaker

  DOI：10.1002/cssc.202300964

  日期：2024.1.8

  A high-throughput experimentation protocol for heterogeneous nitrene transfer (NT) reactions was used to identify replacements for chlorinated solvents. Selected catalysts for NT, including silver supported by N-dentate ligands, dinuclear Rh complexes and Fe/Mn phthalocyanine catalysts, were compared and contrasted using our HTE protocol in terms of both yields and selectivity.

  使用非均相氮宾转移 (NT) 反应的高通量实验方案来确定氯化溶剂的替代品。使用我们的 HTE 协议对选定的 NT 催化剂（包括N齿配体负载的银、双核 Rh 配合物和 Fe/Mn 酞菁催化剂）的产率和选择性进行了比较和对比。
• Catalyst-Controlled Nitrene Transfer by Tuning Metal:Ligand Ratios: Insight into the Mechanisms of Chemoselectivity
  作者：Cale Weatherly、Juliet M. Alderson、John F. Berry、Jason E. Hein、Jennifer M. Schomaker

  DOI：10.1021/acs.organomet.7b00190

  日期：2017.4.24

  Catalyst.controlled, selective nitrene transfer is often challenging when both C-H and C=C bonds are present in a substrate. Interestingly, a simple change in the Ag(I):L ratio (L = bidentate N,N-donor ligand) enables tunable, chemoselective nitrene transfer that favors either C= C bond aziridination using an similar to 1:1 Ag:L ratio (AgLOTf) or insertion into a C-H bond when the Ag:L ratio in the catalyst is 1:2 (AgL2OTO. In this paper, mechanistic studies, coupled with kinetic profiling of the entire reaction course, are employed to examine the reasons for this unusual behavior. Steady-state kinetics were found to be similar for both AgLOTf and AgL2OTf; both complexes yield electronically similar reactive intermediates that engage in nitrene transfer involving formation of a short-lived radical intermediate and barrierless radical recombination. Taken together,, experimental and computational studies point to two effects that control tunable: cherrioSelectiVity: suppression of aziridination as the steric congestion around the silver center is increased in AgL2OTf and a decrease in the rate of C-H insertion with AgLOTf in comparison to AgL2OTE The observation that the sterics of Ag catalysts can be varied, with minor effects on the electronic features of the putative nitrene, has important implications for the development of other silver catalysts that enable tunable, site-selective C-H bond aminations..
• Tunable, Chemoselective Amination <i>via</i> Silver Catalysis
  作者：Jared W. Rigoli、Cale D. Weatherly、Juliet M. Alderson、Brian T. Vo、Jennifer M. Schomaker

  DOI：10.1021/ja406654y

  日期：2013.11.20

  Organic N-containing compounds, including amines, are essential components of many biologically and pharmaceutically important molecules. One strategy for introducing nitrogen into substrates with multiple reactive bonds is to insert a monovalent N fragment (nitrene or nitrenoid) into a C H bond or add it directly to a C=C bond. However, it has been challenging to develop well-defined catalysts capable of promoting predictable and chemoselective aminations solely through reagent control. Herein, we report remarkable chemoselective aminations that employ a single metal (Ag) and a single ligand (phenanthroline) to promote either aziridination or C H insertion by manipulating the coordination geometry of the active catalysts.