trans-7-ethyl-3-oxa-1-aza-bicyclo[4.1.0]heptan-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧氮杂卓类
• 英文名称: trans-7-ethyl-3-oxa-1-aza-bicyclo[4.1.0]heptan-2-one
• 英文别名: (6R,7R)-7-ethyl-3-oxa-1-azabicyclo[4.1.0]heptan-2-one
• 化学式: C₇H₁₁NO₂
• 分子量: 141.17
• InChiKey: JSDYCLJQUSBHHG-LPBDRPKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-7-ethyl-3-oxa-1-aza-bicyclo[4.1.0]heptan-2-one 在 叠氮基三甲基硅烷 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 36.0h， 生成 4-(1-(azido)propyl)-1,3-oxazinan-2-one
  参考文献：
  名称：

  铜催化的不饱和N-对甲氧基氨基甲酸酯的束缚氮杂叠氮化

  摘要：

  氮丙啶是通过铜催化的分子内氮烯加成烯烃而形成的。氨基甲酸酯基团被用作烯烃和腈之间的系链。氮丙啶的后续亲核攻击是使用RSH完成，R 2 NH，N 3 - ，或ROH作为亲核试剂。发现这种添加是区域和立体选择性的。该方法已用于证明其在1，2-二氨基-3-羟基环己烷的区域和立体选择性合成中的效用。这种替代模式存在于天然产品（例如达菲）中。

  DOI：

  10.1021/jo0705014
• 作为产物：
  描述：

  反式-3-己烯-1-醇 在 copper(I) trifluoromethanesulfonate benzene 、 potassium carbonate 、 三乙胺 作用下， 以 乙醚 、 乙腈 为溶剂， 反应 30.0h， 生成 trans-7-ethyl-3-oxa-1-aza-bicyclo[4.1.0]heptan-2-one
  参考文献：
  名称：

  铜催化的不饱和N-对甲氧基氨基甲酸酯的束缚氮杂叠氮化

  摘要：

  氮丙啶是通过铜催化的分子内氮烯加成烯烃而形成的。氨基甲酸酯基团被用作烯烃和腈之间的系链。氮丙啶的后续亲核攻击是使用RSH完成，R 2 NH，N 3 - ，或ROH作为亲核试剂。发现这种添加是区域和立体选择性的。该方法已用于证明其在1，2-二氨基-3-羟基环己烷的区域和立体选择性合成中的效用。这种替代模式存在于天然产品（例如达菲）中。

  DOI：

  10.1021/jo0705014

文献信息

• Copper-Catalyzed Intramolecular C-H Amination
  作者：Dipti N. Barman、Kenneth M. Nicholas

  DOI：10.1002/ejoc.201001160

  日期：2011.2

  The amino-functionalization of tertiary, secondary and benzylic C–H bonds of tethered carbamates and sulfamates by iodosobenzene is catalyzed by CuI-diimine complexes in moderate to good yield. Employing homochiral imine-Cucatalysts affords oxazolidinones and oxathiazinanes with modest enantioselectivity.

  碘代苯对束缚氨基甲酸酯和氨基磺酸酯的叔、仲和苄基 C-H 键的氨基官能化由 CuI-二亚胺配合物催化，产率中等至良好。采用同手性亚胺-Cu 催化剂提供具有适度对映选择性的恶唑烷酮和氧噻嗪烷。
• Synthesis, Characterization, and Variable-Temperature NMR Studies of Silver(I) Complexes for Selective Nitrene Transfer
  作者：Minxue Huang、Joshua R. Corbin、Nicholas S. Dolan、Charles G. Fry、Anastasiya I. Vinokur、Ilia A. Guzei、Jennifer M. Schomaker

  DOI：10.1021/acs.inorgchem.7b00838

  日期：2017.6.5

  solution-state behavior of these catalysts. X-ray structural characterizations were helpful in determining ligand features that promote the formation of monomeric versus dimeric complexes. Variable-temperature 1H and DOSY NMR experiments were especially useful for understanding how the ligand identity influences the nuclearity, coordination number, and fluxional behavior of silver(I) complexes in solution

  氮供体配体支持的一系列银配合物通过氮转移催化C═C和C–H键转变为有价值的C–N键。在胺化过程中实现高化学选择性和位点选择性的能力需要了解这些催化剂的固态和溶液态行为。X射线结构表征有助于确定促进单体与二聚体复合物形成的配体特征。可变温度1 H和DOSY NMR实验对于了解配体身份如何影响溶液中银（I）配合物的核度，配位数和通量行为特别有用。这些见解对于开发改进的配体设计是有价值的。
• 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..