(3S,7aR)-7a-methyl-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one | 137869-70-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3S,7aR)-7a-methyl-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one
• 英文别名: (3S,7aR)-7a-methyl-3-phenyl-2,3,6,7-tetrahydropyrrolo[2,1-b][1,3]oxazol-5-one
• CAS: 137869-70-6
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: JVEHIYMWPAQEIR-DGCLKSJQSA-N

物化性质

• 熔点：
  125 °C
• 沸点：
  357.82°C (rough estimate)
• 密度：
  1.0960 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xn
• 安全说明：
  S36/37
• 危险类别码：
  R20/21/22

反应信息

• 作为反应物：
  描述：

  (3S,7aR)-7a-methyl-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one 生成 methyl (1R,2R,4R,7S)-1-methyl-5-oxo-7-phenyl-9-oxa-6-azatricyclo[4.3.0.02,4]nonane-4-carboxylate
  参考文献：
  名称：

  An asymmetric synthesis of novel aminocyclopropyl carboxylic acids (ACC)

  摘要：

  将手性双环内酰胺 2 环丙烷化，然后去除手性助剂并进行 Curtius 重排，就可以得到标题化合物，纯度大于 99%。

  DOI：

  10.1039/c39950000141
• 作为产物：
  描述：

  L-苯甘氨醇 、 乙酰丙酸 以 甲苯 为溶剂， 以82%的产率得到(3S,7aR)-7a-methyl-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one
  参考文献：
  名称：

  Single and Double Diastereoselection in Azomethine Ylide Cycloaddition Reactions with Unsaturated Chiral Bicyclic Lactams

  摘要：

  Double diastereoselectivity data were analyzed to provide insight into the structural features that influence pi-facial selectivity in 1,3-dipolar cycloadditions of chiral and achiral azomethine ylides to chiral, unsaturated bicyclic lactams. Three major steric contributions to the differences in stability (Delta Delta G(double dagger)) between competing cycloaddition transition states were identified. The first major set of steric interactions involve that between the dipoles and the substituents on the left hemisphere (R(2)) and concave faces of the bicyclic lactams. This effectively hindered both alpha- and beta-approaches in the nonextended transition states shown in Figure 1. The second major steric interaction was provided by the nonbonded interactions (i) between the R(1) angular substituent on the bicyclic lactam and the pi-system of the dipole as shown in Figures 3 and 4. This interaction was shown to be very significant, causing reversal in pi-facial attack of chiral and achiral dipoles when the angular substituent is changed from phenyl or methyl to hydrogen. The high diastereoselectivity observed now opens a route to highly substituted chiral, nonracemic pyrrolidines.

  DOI：

  10.1021/jo9600870

文献信息

• Concise synthesis of indolizidines: total synthesis of (−)-coniceine
  作者：Michael D. Groaning、A. I. Meyers

  DOI：10.1039/b002621m

  日期：——

  The Ti-mediated allylsilane addition to bicyclic lactams occurs with high stereoselectivity and combined with a ring closure metathesis provides the title compounds in high ee.

  Ti 介导的烯丙基硅烷与双环内酰胺的加成具有高立体选择性，并与闭环复分解相结合，提供了高 ee 的标题化合物。
• Synthesis of enantiomerically pure hydrinden-2-ones and benz[e]inden-2-ones via asymmetric alkylations of chiral bicyclic lactams
  作者：Lawrence Snyder、A. I. Meyers

  DOI：10.1021/jo00078a032

  日期：1993.12

  A route to the titled compounds in >99 % ee was achieved from sequential diastereoselective alkylations of chiral, nonracemic bicyclic lactams 6 and 15. An intramolecular addition of the organolithium species derived from 17a-c and 28a-d gave, after hydrolysis, diketones 25a-c and 30a-d, which were cyclized to the titled compounds 4a-c and 31a-d. As an example of the versatility of this method, the ABC ring system of the triterpene stelliferin A, isolated from marine organisms, was prepared in high enantiomeric excess.
• Asymmetric Lewis Acid-Catalyzed Addition of a Ketene Dithioacetal to a Chiral Bicyclic Lactam. Formation of Cyclobutanopyrrolidinones. A New Class of GABA Derivatives
  作者：A. I. Meyers、Matt A. Tschantz、Gregory P. Brengel

  DOI：10.1021/jo00119a012

  日期：1995.7

  Additions to unsaturated chiral lactams 8 using methylenedithiolane, gave very high endo-selectivity of the cyclobutane adducts (2 + 2 addition) 13, 16. Removal of the phenylglycinol auxiliary by reductive cleavage produced the title compound (+)-20 in very high (>99%) enantiomeric excess. Absolute stereochemistry of the cyclobutanopyrrolidinone, containing three contiguous stereocenters, was confirmed by X-ray crystallography.
• Asymmetric conjugate additions to chiral bicyclic lactams. Synthesis of aracemic trans-2,3-disubstituted pyrrolidines
  作者：A. I. Meyers、Lawrence Snyder

  DOI：10.1021/jo00040a018

  日期：1992.7

  The trans-2,3-disubstituted pyrrolidine moiety, found in the pyrrolizidine alkaloids as well as other natural products, has been accessed from the alpha,beta-unsaturated bicyclic lactams 1d and 10. Conjugate addition of lower order cyanocuprates to lactams 1d and 10 resulted in endo entry of the cuprate with high diastereoselectivity. Other cuprates were investigated and resulted in diminished or opposite stereoselectivities. Further transformation of the beta-substituted lactams provided the title compounds in good overall yield and high enantiomeric excess.
• Single and Double Diastereoselection in Azomethine Ylide Cycloaddition Reactions with Unsaturated Chiral Bicyclic Lactams
  作者：Andrew H. Fray、A. I. Meyers

  DOI：10.1021/jo9600870

  日期：1996.1.1

  Double diastereoselectivity data were analyzed to provide insight into the structural features that influence pi-facial selectivity in 1,3-dipolar cycloadditions of chiral and achiral azomethine ylides to chiral, unsaturated bicyclic lactams. Three major steric contributions to the differences in stability (Delta Delta G(double dagger)) between competing cycloaddition transition states were identified. The first major set of steric interactions involve that between the dipoles and the substituents on the left hemisphere (R(2)) and concave faces of the bicyclic lactams. This effectively hindered both alpha- and beta-approaches in the nonextended transition states shown in Figure 1. The second major steric interaction was provided by the nonbonded interactions (i) between the R(1) angular substituent on the bicyclic lactam and the pi-system of the dipole as shown in Figures 3 and 4. This interaction was shown to be very significant, causing reversal in pi-facial attack of chiral and achiral dipoles when the angular substituent is changed from phenyl or methyl to hydrogen. The high diastereoselectivity observed now opens a route to highly substituted chiral, nonracemic pyrrolidines.