4-(but-3-en-1-yl)oxazolidin-2-one | 224561-62-0

• 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: 4-(but-3-en-1-yl)oxazolidin-2-one
• 英文别名: 4-(but-3-enyl)oxazolidin-2-one；4-But-3-enyl-1,3-oxazolidin-2-one
• CAS: 224561-62-0
• 化学式: C₇H₁₁NO₂
• mdl: MFCD19218762
• 分子量: 141.17
• InChiKey: JLWGNLNFMLCMRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(but-3-en-1-yl)oxazolidin-2-one 在 sodium hypochlorite 作用下， 以 氯仿 、 水 为溶剂， 以68%的产率得到N-chloro-4-(but-3-enyl)oxazolidin-2-one
  参考文献：
  名称：

  烯烃N-氯吡咯烷酮，N-氯琥珀酰亚胺和N-氯恶唑烷酮的光解：环羧酰胺基，亚胺基和氨基甲酰基在分子内反应中的反应性

  摘要：

  制备N-氯-烯基吡咯烷酮，N-氯-烯基琥珀酰亚胺和N-氯-烯基恶唑烷酮作为烯属环羧酰胺基，亚胺基和氨基甲酸酯基团的前体，这些化合物仅通过它们的平面或轻微扭曲（30-35°）π分子内发生反应。N状态（烯丙基氢的1,5-转移，5- exo或6- exo环化分别产生双环[2.2.1]氮杂庚烷和双环[3.2.1]氮杂辛烷骨架），这些分子内反应是平面无法获得的Σ ñ状态。他们的光解作用产生的产物独特地是由这些氮自由基的分子间反应产生的（添加到外部烯烃中，从溶剂中提取氢，烯丙基氢提取）。用N-氯-链烯基吡咯烷酮和N-氯-链烯基恶唑烷酮，观察到通过5-外显环化反应生成双环[3.3.0]氮杂辛烷衍生物的分子内反应。在这两种情况下，无论是Π Ñ和Σ Ñ环状酰胺基自由基的状态允许5 -外环化轨道重叠。

  DOI：

  10.1016/s0040-4020(98)01158-2
• 作为产物：
  描述：

  tert-butyl 1-hydroxyhex-5-en-2-ylcarbamate 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 2.75h， 以97%的产率得到4-(but-3-en-1-yl)oxazolidin-2-one
  参考文献：
  名称：

  Pd-Catalyzed Carboamination of Oxazolidin-2-ones: A Stereoselective Route to trans-2,5-Disubstituted Pyrrolidines

  摘要：

  Palladium-catalyzed carboamination reactions between aryl bromides and 4-(but-3-enyl)-substituted oxazolidin-2-ones are described. These transformations afford bicyclic oxazolidin-2-one derivatives that can be converted to trans-2,5-disubstituted pyrrolidines in one step. The starting materials are easily prepared from amino acid precursors, and products that contain up to three stereocenters are generated with >20:1 dr.

  DOI：

  10.1021/ol1006828

文献信息

• Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-<i>Endo</i> Cyclization of α-Carbamoyl Radicals
  作者：Xinqiang Fang、Kun Liu、Chaozhong Li

  DOI：10.1021/ja9082649

  日期：2010.2.24

  The iodine-atom-transfer 8-endo cyclization of alpha-carbamoyl radicals was investigated experimentally and theoretically. With the aid of Mg(ClO4)(2) and a bis(oxazoline) ligand, N-ethoxycarbonyl-substituted N-(pent-4-enyl)-2-iodoalkanamides underwent 8-endo cyclization leading to the formation of only the corresponding 3,5-trans-substituted azocan-2-ones in excellent yields Similarly, the BF3 center dot OEt2/H2O-promoted reactions of N-ethoxycarbonyl-N-(2-allylaryl)-2-iodoalkanamides afforded exclusively the benzazocanone products with a 3,5-cis configuration in high yields The bidentate chelation of substrate radicals not only significantly improved the efficiency of cyclization but also resulted in the change of stereochemistry of azocanone products from 3,8-trans to 3,8-cis Theoretical calculations at the UB3LYP/6-31G* level revealed that the cyclization of N-carbonyl-substituted alpha-carbamoyl radicals occurs via the E-conformational transition states without the presence of a Lewis acid. On the other hand, the cyclization proceeds via the Z-conformational transition states when the substrates form the bidentate chelation with a Lewis acid In both cases, the 8-endocyclization is always fundamentally preferred over the corresponding 7-exo cyclization The complexed radicals having the more rigid conformations also allow the better stereochemical control in the iodine-atom-abstraction step To further understand the reactivity of alpha-carbamoyl radicals, the competition between the 8-endo and 5-exo cyclization was also studied The results demonstrated that the 8-endo cyclization is of comparable rate to the corresponding 5-exo cyclization for alpha-carbamoyl radicals with fixed Z-conformational transition states As a comparison, the 8-endo mode is fundamentally preferred over the 5-exo mode in the cyclization of INIH-amide substrates because the latter requires the Z-conformational transition states, whereas the former proceeds via the more stable E-conformational transition states.
• Pd-Catalyzed Carboamination of Oxazolidin-2-ones: A Stereoselective Route to <i>trans</i>-2,5-Disubstituted Pyrrolidines
  作者：Georgia S. Lemen、John P. Wolfe

  DOI：10.1021/ol1006828

  日期：2010.5.21

  Palladium-catalyzed carboamination reactions between aryl bromides and 4-(but-3-enyl)-substituted oxazolidin-2-ones are described. These transformations afford bicyclic oxazolidin-2-one derivatives that can be converted to trans-2,5-disubstituted pyrrolidines in one step. The starting materials are easily prepared from amino acid precursors, and products that contain up to three stereocenters are generated with >20:1 dr.
• Photolysis of olefinic N-chloropyrrolidinones, N-chlorosuccinimides and N-chloro-oxazolidinones: Reactivity of cyclic carboxamidyl, imidyl and carbamyl radicals in intramolecular reactions
  作者：Benoit Daoust、Jean Lessard

  DOI：10.1016/s0040-4020(98)01158-2

  日期：1999.3

  carboxamidyl, imidyl and carbamyl radicals constrained to undergo intramolecular reactions uniquely via their planar or slightly twisted (30–35°) ΠN state (1,5-transfer of an allylic hydrogen, 5-exo or 6-exo cyclization to give bicyclo[2.2.1]azaheptane and bicyclo[3.2.1]azaoctane skeletons respectively), those intramolecular reactions being unaccessible to the planar ΣN state. Their photolysis gave products

  制备N-氯-烯基吡咯烷酮，N-氯-烯基琥珀酰亚胺和N-氯-烯基恶唑烷酮作为烯属环羧酰胺基，亚胺基和氨基甲酸酯基团的前体，这些化合物仅通过它们的平面或轻微扭曲（30-35°）π分子内发生反应。N状态（烯丙基氢的1,5-转移，5- exo或6- exo环化分别产生双环[2.2.1]氮杂庚烷和双环[3.2.1]氮杂辛烷骨架），这些分子内反应是平面无法获得的Σ ñ状态。他们的光解作用产生的产物独特地是由这些氮自由基的分子间反应产生的（添加到外部烯烃中，从溶剂中提取氢，烯丙基氢提取）。用N-氯-链烯基吡咯烷酮和N-氯-链烯基恶唑烷酮，观察到通过5-外显环化反应生成双环[3.3.0]氮杂辛烷衍生物的分子内反应。在这两种情况下，无论是Π Ñ和Σ Ñ环状酰胺基自由基的状态允许5 -外环化轨道重叠。

表征谱图