(3S-顺式)-(-)-3-苯基四氢吡咯并-[2,1-b]-恶唑-5(6H)-酮 | 122383-34-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (3S-顺式)-(-)-3-苯基四氢吡咯并-[2,1-b]-恶唑-5(6H)-酮
• 中文别名: (3S-顺)-(-)-3-苯基四氢吡咯并-[2,1-B]噁唑-5(6H)-酮
• 英文名称: (3S,7aR)-5-oxo-3-phenyl-2,3,5,6,7,7a-hexahydropyrrolo<2,1-b>oxazole
• 英文别名: (3S,7aR)-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one；(3S,7aR)-3-phenyl-3,6,7,7a-tetrahydro-2H-pyrrolo[2,1-b][1,3]oxazol-5-one
• CAS: 122383-34-0
• 化学式: C₁₂H₁₃NO₂
• 分子量: 203.241
• InChiKey: CQPBRZXBXFZYBD-ZYHUDNBSSA-N

物化性质

• 熔点：
  76-80 °C
• 沸点：
  341.55°C (rough estimate)
• 密度：
  1.1255 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 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-顺式)-(-)-3-苯基四氢吡咯并-[2,1-b]-恶唑-5(6H)-酮 在 palladium on activated charcoal 苯基溴化硒 、 双氧水 、 ammonium formate 、 lithium hexamethyldisilazane 作用下， 反应 6.25h， 生成 (3S,7R,7aR)-3,7-diphenyl-3,6,7,7a-tetrahydro-2H-pyrrolo[2,1-b][1,3]oxazol-5-one
  参考文献：
  名称：

  The synthesis of aracemic 4-substituted pyrrolidinones and 3-substituted pyrrolidines. An asymmetric synthesis of (-)-rolipram

  摘要：

  Conjugate additions of RCuCNLi to the chiral alpha,beta-unsaturated lactam 4 gives almost exclusive exo addition-a reversal in stereochemistry when cuprates were added to chiral lactam 1. The lactams 5 were transformed into 4-substituted pyrrolidinones 8 via a three-step sequence which involved decarbalkoxylation, silane reduction and metal-ammonia benzylamine cleavage. The chemical yields as well as the enantiomeric purity were very high for this process. As an example of the usefulness of this scheme, the antidepressant (-)-Rolipram was prepared in good overall yield. Furthermore, the bicyclic lactams 6 were readily transformed, using alane as the reducing agent, to 3-substituted pyrrolidines 11. Absolute configurations of 8 and 11 were confirmed by comparison with literature assignments which also gave strong support to the facial addition of the cuprates to 4.

  DOI：

  10.1021/jo00053a012
• 作为产物：
  描述：

  (S)-N-(2-(tert-butyldimethylsilyloxy)-1-phenylethyl)prop-2-en-1-amine 在 二氯(邻异丙氧基苯基亚甲基)(三环己基膦)钌 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 间二甲苯 为溶剂， 反应 18.0h， 生成 (3S-顺式)-(-)-3-苯基四氢吡咯并-[2,1-b]-恶唑-5(6H)-酮
  参考文献：
  名称：

  通过钌催化的串联闭环复分解/异构化/ N-酰基亚胺基环化序列合成杂环

  摘要：

  串联自行车：在标题反应中，在闭环易位过程中产生的双键异构化，生成反应性亚胺基中间体，这些中间体与束缚的杂原子和碳亲核试剂进行分子内环化反应。以此方式，可以制备一系列生物学上令人感兴趣的杂环化合物，包括用于抗寄生虫天然产物毒品的全合成的已知前体。

  DOI：

  10.1002/anie.201100417

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。
• <i>N</i>-Trialkylsilyl Bistrifluoromethanesulfonimides (R₃SiNTf₂) Are Powerful Catalysts for the Highly Efficient α-Amido Alkylation Reactions of Silicon-Based Nucleophiles
  作者：Raja Ben Othman、Till Bousquet、Mohamed Othman、Vincent Dalla

  DOI：10.1021/ol052357j

  日期：2005.11.1

  In situ formed N-trialkylsilyl bistrifluoromethanesulforlimides (R3SiNTf2) species have been shown to efficiently catalyze the nucleophilic substitution reactions of chiral 5-oxypyrrolidin-2-ones by silicon-based nucleophiles. The reaction rates were significantly accelerated in comparison to the cases where the usual triflate catalysts are used. Adducts were obtained in high yields and usual stereoselectivities within short reaction times, and the process was compatible with a semipreparative scale.
• 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.
• A facile synthesis of chiral bicyclic lactams utilized in the formation of chiral quaternary carbon compounds
  作者：A. I. Meyers、Bruce A. Lefker、Thomas J. Sowin、Larry J. Westrum

  DOI：10.1021/jo00278a053

  日期：1989.8
• A Synthesis of Enantiomerically Pure 3- and 3,3-Disubstituted Pyrrolidines
  作者：Larry J. Westrum、A.I. Meyers

  DOI：10.1016/s0040-4039(00)79942-4

  日期：1994.2

  Enantiomerically pure bicyclic lactam 1, derived from (S)-phenylglycinol, underwent diastereoselective mono- and dialkylation affording substituted lactams 2 and 3 bearing tertiary and quaternary stereocenters. Reduction with LiAlH4 furnished N-(2'-hydroxy-1'-phenylethyl) pyrrolidines 4 which were efficiently debenzylated by catalytic hydrogenolysis to afford enantiomerically pure 3-mono- and 3,3-disubstituted pyrrolidines 5.